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Sample records for cationic gold clusters

  1. The adsorption of helium atoms on small cationic gold clusters.

    Science.gov (United States)

    Goulart, Marcelo; Gatchell, Michael; Kranabetter, Lorenz; Kuhn, Martin; Martini, Paul; Gitzl, Norbert; Rainer, Manuel; Postler, Johannes; Scheier, Paul; Ellis, Andrew M

    2018-04-04

    Adducts formed between small gold cluster cations and helium atoms are reported for the first time. These binary ions, Aun+Hem, were produced by electron ionization of helium nanodroplets doped with neutral gold clusters and were detected using mass spectrometry. For a given value of n, the distribution of ions as a function of the number of added helium atoms, m, has been recorded. Peaks with anomalously high intensities, corresponding to so-called magic number ions, are identified and interpreted in terms of the geometric structures of the underlying Aun+ ions. These features can be accounted for by planar structures for Aun+ ions with n ≤ 7, with the addition of helium having no significant effect on the structures of the underlying gold cluster ions. According to ion mobility studies and some theoretical predictions, a 3-D structure is expected for Au8+. However, the findings for Au8+ in this work are more consistent with a planar structure.

  2. Gold cluster carbonyls: saturated adsorption of CO on gold cluster cations, vibrational spectroscopy, and implications for their structures.

    Science.gov (United States)

    Fielicke, André; von Helden, Gert; Meijer, Gerard; Pedersen, David B; Simard, Benoit; Rayner, David M

    2005-06-15

    We report on the interaction of carbon monoxide with cationic gold clusters in the gas phase. Successive adsorption of CO molecules on the Au(n)(+) clusters proceeds until a cluster size specific saturation coverage is reached. Structural information for the bare gold clusters is obtained by comparing the saturation stoichiometry with the number of available equivalent sites presented by candidate structures of Au(n)(+). Our findings are in agreement with the planar structures of the Au(n)(+) cluster cations with n < or = 7 that are suggested by ion mobility experiments [Gilb, S.; Weis, P.; Furche, F.; Ahlrichs, R.; Kappes, M. M. J. Chem. Phys. 2001, 116, 4094]. By inference we also establish the structure of the saturated Au(n)(CO)(m)(+) complexes. In certain cases we find evidence suggesting that successive adsorption of CO can distort the metal cluster framework. In addition, the vibrational spectra of the Au(n)(CO)(m)(+) complexes in both the CO stretching region and in the region of the Au-C stretch and the Au-C-O bend are measured using infrared photodepletion spectroscopy. The spectra further aid in the structure determination of Au(n)(+), provide information on the structure of the Au(n)(+)-CO complexes, and can be compared with spectra of CO adsorbates on deposited clusters or surfaces.

  3. Communication: CO oxidation by silver and gold cluster cations: Identification of different active oxygen species

    International Nuclear Information System (INIS)

    Popolan, Denisia M.; Bernhardt, Thorsten M.

    2011-01-01

    The oxidation of carbon monoxide with nitrous oxide on mass-selected Au 3 + and Ag 3 + clusters has been investigated under multicollision conditions in an octopole ion trap experiment. The comparative study reveals that for both gold and silver cations carbon dioxide is formed on the clusters. However, whereas in the case of Au 3 + the cluster itself acts as reactive species that facilitates the formation of CO 2 from N 2 O and CO, for silver the oxidized clusters Ag 3 O x + (n= 1-3) are identified as active in the CO oxidation reaction. Thus, in the case of the silver cluster cations N 2 O is dissociated and one oxygen atom is suggested to directly react with CO, whereas a second kind of oxygen strongly bound to silver is acting as a substrate for the reaction.

  4. Communication: CO oxidation by silver and gold cluster cations: Identification of different active oxygen species

    Science.gov (United States)

    Popolan, Denisia M.; Bernhardt, Thorsten M.

    2011-03-01

    The oxidation of carbon monoxide with nitrous oxide on mass-selected Au3+ and Ag3+ clusters has been investigated under multicollision conditions in an octopole ion trap experiment. The comparative study reveals that for both gold and silver cations carbon dioxide is formed on the clusters. However, whereas in the case of Au3+ the cluster itself acts as reactive species that facilitates the formation of CO2 from N2O and CO, for silver the oxidized clusters Ag3Ox+ (n = 1-3) are identified as active in the CO oxidation reaction. Thus, in the case of the silver cluster cations N2O is dissociated and one oxygen atom is suggested to directly react with CO, whereas a second kind of oxygen strongly bound to silver is acting as a substrate for the reaction.

  5. Investigation of Carbon Monoxide Adsorption on Cationic Gold- Palladium Clusters

    Science.gov (United States)

    Chen, Yang-Mei; Kuang, Xiao-Yu; Sheng, Xiao-Wei; Wang, Huai-Qian; Shao, Peng; Zhong, Min-Ming

    2013-11-01

    Density functional calculations have been performed for the carbon monoxide molecule adsorption on AunPd+m(n+m ≤ 6) clusters. In the process of CO adsorption, small Au clusters and Pd clusters tend to be an Au atom and three Pd atoms adsorption, respectively. For the mixed Au-Pd clusters, an Au atom, a Pd atom, two atoms consisted of an Au atom and a Pd atom, two Pd atoms, and three Pd atoms adsorption structures are displayed. The highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) gaps and natural bond orbital charge population are calculated. Moreover, CO adsorption energy, CO stretching frequency, and CO bond length (upon adsorption) are also analysed in detail. The results predict that the adsorption strength of Au clusters with CO and the C-O vibration strength is enhanced and reduced after doping of Pd in the AunPdmCO+ complexes, respectively

  6. A density functional study of carbon monoxide adsorption on small cationic, neutral, and anionic gold clusters

    Science.gov (United States)

    Wu, X.; Senapati, L.; Nayak, S. K.; Selloni, A.; Hajaligol, M.

    2002-08-01

    CO adsorption on small cationic, neutral, and anionic Aun (n=1-6) clusters has been investigated using density functional theory in the generalized gradient approximation. Among various possible CO adsorption sites, the on-top (one-fold coordinated) is found to be the most favorable one, irrespective of the charge state of the cluster. In addition, planar structures are preferred by both the bare and the CO-adsorbed clusters. The adsorption energies of CO on the cationic clusters are generally greater than those on the neutral and anionic complexes, and decrease with size. The adsorption energies on the anions, instead, increase with cluster size and reach a local maximum at Au5CO-, in agreement with recent experiment. The differences in adsorption energies for the different charge states decrease with increasing cluster size.

  7. Binding energy and preferred adsorption sites of CO on gold and silver-gold cluster cations: adsorption kinetics and quantum chemical calculations.

    Science.gov (United States)

    Neumaier, Marco; Weigend, Florian; Hampe, Oliver; Kappes, Manfred M

    2008-01-01

    We revisit the reactivity of trapped pure gold (Au(n)+, n cations (Ag(m)Au(n)+, m + n carbon monoxide as studied in a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. The experimental results are discussed in terms of ab initio computations which provide a comprehensive picture of the chemical binding behaviour (like binding energy, adsorption sites, associated vibrational frequencies) of CO to the noble metal as a function of cluster size and composition. Starting from results for pure gold cluster cations for which an overall decrease of CO binding energy with increasing cluster size was experimentally observed--from about 1.09 +/- 0.1 eV (for n = 6) to below 0.65 +/- 0.1 eV (for n > 26) we demonstrate that metal--CO bond energies correlate with the total electron density and with the energy of the lowest unoccupied molecular orbital (LUMO) on the bare metal cluster cation as obtained by density functional theory (DFT) computations. This is a consequence of the predominantly sigma-donating character of the CO-M bond. Further support for this concept is found by contrasting the predictions of binding energies to the experimental results for small alloy cluster cations (Ag(m)Au(n)+, 4 < m + n < 7) as a function of composition. Here, binding energy drops with increasing silver content, while CO still binds always in a head-on fashion to a gold atom. Finally we show how the CO stretch frequency of Ag(m)Au(n)CO+ may be used to identify possible adsorption sites and pre-screen favorable isomers.

  8. Probing the structural and electronic properties of cationic rubidium-gold clusters: [AunRb]+ (n = 1-10)

    Science.gov (United States)

    Zhao, Ya-Ru; Zhang, Hai-Rong; Qian, Yu; Duan, Xu-Chao; Hu, Yan-Fei

    2016-03-01

    Density functional theory has been applied to study the geometric structures, relative stabilities, and electronic properties of cationic [AunRb]+ and Aun + 1+ (n = 1-10) clusters. For the lowest energy structures of [AunRb]+ clusters, the planar to three-dimensional transformation is found to occur at cluster size n = 4 and the Rb atoms prefer being located at the most highly coordinated position. The trends of the averaged atomic binding energies, fragmentation energies, second-order difference of energies, and energy gaps show pronounced even-odd alternations. It indicated that the clusters containing odd number of atoms maintain greater stability than the clusters in the vicinity. In particular, the [Au6Rb]+ clusters are the most stable isomer for [AunRb]+ clusters in the region of n = 1-10. The charges in [AunRb]+ clusters transfer from the Rb atoms to Aun host. Density of states revealed that the Au-5d, Au-5p, and Rb-4p orbitals hardly participated in bonding. In addition, it is found that the most favourable channel of the [AunRb]+ clusters is Rb+ cation ejection. The electronic localisation function (ELF) analysis of the [AunRb]+ clusters shown that strong interactions are not revealed in this study.

  9. Reactions of mixed silver-gold cluster cations AgmAun+ (m+n=4,5,6) with CO: Radiative association kinetics and density functional theory computations

    International Nuclear Information System (INIS)

    Neumaier, Marco; Weigend, Florian; Hampe, Oliver; Kappes, Manfred M.

    2006-01-01

    Near thermal energy reactive collisions of small mixed metal cluster cations Ag m Au n + (m+n=4, 5, and 6) with carbon monoxide have been studied in the room temperature Penning trap of a Fourier transform ion-cyclotron-resonance mass spectrometer as a function of cluster size and composition. The tetrameric species AgAu 3 + and Ag 2 Au 2 + are found to react dissociatively by way of Au or Ag atom loss, respectively, to form the cluster carbonyl AgAu 2 CO + . In contrast, measurements on a selection of pentamers and hexamers show that CO is added with absolute rate constants that decrease with increasing silver content. Experimentally determined absolute rate constants for CO adsorption were analyzed using the radiative association kinetics model to obtain cluster cation-CO binding energies ranging from 0.77 to 1.09 eV. High-level ab initio density functional theory (DFT) computations identifying the lowest-energy cluster isomers and the respective CO adsorption energies are in good agreement with the experimental findings clearly showing that CO binds in a ''head-on'' fashion to a gold atom in the mixed clusters. DFT exploration of reaction pathways in the case of Ag 2 Au 2 + suggests that exoergicities are high enough to access the minimum energy products for all reactive clusters probed

  10. Reactions of mixed silver-gold cluster cations AgmAun+ (m+n=4,5,6) with CO: Radiative association kinetics and density functional theory computations

    Science.gov (United States)

    Neumaier, Marco; Weigend, Florian; Hampe, Oliver; Kappes, Manfred M.

    2006-09-01

    Near thermal energy reactive collisions of small mixed metal cluster cations AgmAun+ (m +n=4, 5, and 6) with carbon monoxide have been studied in the room temperature Penning trap of a Fourier transform ion-cyclotron-resonance mass spectrometer as a function of cluster size and composition. The tetrameric species AgAu3+ and Ag2Au2+ are found to react dissociatively by way of Au or Ag atom loss, respectively, to form the cluster carbonyl AgAu2CO+. In contrast, measurements on a selection of pentamers and hexamers show that CO is added with absolute rate constants that decrease with increasing silver content. Experimentally determined absolute rate constants for CO adsorption were analyzed using the radiative association kinetics model to obtain cluster cation-CO binding energies ranging from 0.77to1.09eV. High-level ab initio density functional theory (DFT) computations identifying the lowest-energy cluster isomers and the respective CO adsorption energies are in good agreement with the experimental findings clearly showing that CO binds in a "head-on" fashion to a gold atom in the mixed clusters. DFT exploration of reaction pathways in the case of Ag2Au2+ suggests that exoergicities are high enough to access the minimum energy products for all reactive clusters probed.

  11. Theoretical study of oxygen adsorption on pure Au-n+1(+) and doped MAun+ cationic gold clusters for M = Ti, Fe and n=3-7

    DEFF Research Database (Denmark)

    Torres, M. Begona; Fernandez Sanchez, Eva; Balbas, Luis C.

    2008-01-01

    A comparative study of the adsorption of an O-2 molecule on pure Au-n+1(+) and doped MAun+ cationic gold clusters for n = 3-7 and M = Ti, Fe is presented. The simultaneous adsorption of two oxygen atoms also was studied. This work was performed by means of first principles calculations based...... with adsorption energies of 0.56 and 0.69 eV, respectively. The ground-state geometry of Au-n(+) is almost unperturbed after O-2 adsorption. The electronic charge flows towards O-2 when the molecule is adsorbed in bridge positions and towards the gold cluster when O-2 is adsorbed on top of An atoms, and both...... with size n are rationalized in terms of O-O and O-M bond distances, as well as charge transfer between oxygen and cluster substrates. The spin multiplicity of those (MAunO2+)(ad) complexes with the highest O-2 adsorption energy is a maximum (minimum) for M = Fe (Ti), corresponding to parallel (anti...

  12. On the origin of bonding and vibrational frequency shifts for CO adsorbed on neutral, cationic and anionic gold clusters

    International Nuclear Information System (INIS)

    Bagus, P S; Pacchioni, G

    2008-01-01

    We report a detailed analysis of the electronic mechanisms which determine the bond strength and the vibrational frequency of CO molecules adsorbed on neutral or charged gold nanoparticles. To this end we have considered a simple cluster model, Au 5 CO q (q = +1, 0, -1), and decomposed the Au-CO interaction energy into the sum of various contributions according to a Constrained Space Orbital Variation approach. While the adsorption energy is relatively insensitive to the value of q, the C-O stretch frequency, ω e (CO), changes substantially, and allows the use of this molecule as a direct probe of the gold oxidation state. The results show that two major terms contribute to the red or blue shift of ω e (CO) as a function of q: the interaction with the electric field associated to the charged nanoparticle (Stark effect) and the Au → CO Φ back donation. The CO → Au σ donation is about half as important as the Φ back-donation and all other terms are much less important

  13. Cyanide leaching of Au/CeO2: highly active gold clusters for 1,3-butadiene hydrogenation

    NARCIS (Netherlands)

    Guan, Y.; Hensen, E.J.M.

    2009-01-01

    Ceria-supported gold catalysts before and after leaching by NaCN were investigated by X-ray absorption spectroscopy at the Au LIII edge. After gold leaching, isolated gold cations remain in close interaction with the support. These ions form an ideal precursor to very small clusters of a few gold

  14. Effect of alkali metal cations on anodic dissolution of gold in cyanide solutions. Potentiodynamic measurement

    International Nuclear Information System (INIS)

    Bek, R.Yu.; Rogozhnikov, N.A.; Kosolapov, G.V.

    1998-01-01

    It is shown that gold dissolution rate in cyanic solutions in Li + , Na + , K + , Cs + cation series increases basically and decreases under cation concentration increasing. Cation effect on current value is caused by cations drawing in dense layer. A model of dense part of double layer with two Helmholtz planes (anion and cation) is suggested. Effect of nature and concentration of alkali metal cations on gold dissolution rate is explained on the base of the model [ru

  15. Gold for the generation and control of fluxional barbaralyl cations.

    Science.gov (United States)

    McGonigal, Paul R; de León, Claudia; Wang, Yahui; Homs, Anna; Solorio-Alvarado, César R; Echavarren, Antonio M

    2012-12-21

    The frog prince with his two identities pales in comparison with the shape-shifting barbaralyl cation, which exists as a mixture of 181,400 degenerate forms. Gold-catalyzed cycloisomerizations of 7-alkynyl cyclohepta-1,3,5-trienes were found to proceed via fluxional barbaralyl intermediates. The evolution of the intermediates into 1- or 2-substituted indenes could be controlled by the choice of gold complex. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. sp magnetism in clusters of gold thiolates

    International Nuclear Information System (INIS)

    Ayuela, A; Hernando, A; Echenique, P M; Crespo, P; García, M A

    2012-01-01

    Using first-principles calculations, we consider the bond between thiolate and small Au clusters, with particular emphasis on the resulting magnetic moment. The moment of pure gold clusters is 1 μ B for clusters with an odd number of Au atoms and zero for those with an even number. The addition of the thiolate, having an odd number of electrons itself, shifts the phase of the odd-even oscillations so that particles with an even number of Au atoms now have unit moment. Surprisingly, gold thiolate exhibits a dramatic and non-intuitive distribution of charge and spin moment. Our results show that the S-Au bond is such that sulfur does not get charge and an electron is transferred to the Au cluster. This extra electron is mainly sp in character and resides in an electronic shell below the Au surface. The calculations suggest that any thiolate-induced magnetism occurs in the gold nanoparticle and not the thiolate, and can be controlled by modifying the thiolate coverage. (paper)

  17. Site-Specific Biomolecule Labeling with Gold Clusters

    Science.gov (United States)

    Ackerson, Christopher J.; Powell, Richard D.; Hainfeld, James F.

    2013-01-01

    Site-specific labeling of biomolecules in vitro with gold clusters can enhance the information content of electron cryomicroscopy experiments. This chapter provides a practical overview of well-established techniques for forming biomolecule/gold cluster conjugates. Three bioconjugation chemistries are covered: Linker-mediated bioconjugation, direct gold–biomolecule bonding, and coordination-mediated bonding of nickel(II) nitrilotriacetic acid (NTA)-derivatized gold clusters to polyhistidine (His)-tagged proteins. PMID:20887859

  18. Site-Specific Biomolecule Labeling with Gold Clusters

    OpenAIRE

    Ackerson, Christopher J.; Powell, Richard D.; Hainfeld, James F.

    2010-01-01

    Site-specific labeling of biomolecules in vitro with gold clusters can enhance the information content of electron cryomicroscopy experiments. This chapter provides a practical overview of well-established techniques for forming biomolecule/gold cluster conjugates. Three bioconjugation chemistries are covered: Linker-mediated bioconjugation, direct gold–biomolecule bonding, and coordination-mediated bonding of nickel(II) nitrilotriacetic acid (NTA)-derivatized gold clusters to polyhistidine (...

  19. Cyanide leaching of Au/CeO2: highly active gold clusters for 1,3-butadiene hydrogenation.

    Science.gov (United States)

    Guan, Y; Hensen, E J M

    2009-11-07

    Ceria-supported gold catalysts before and after leaching by NaCN were investigated by X-ray absorption spectroscopy at the Au L(III) edge. After gold leaching, isolated gold cations remain in close interaction with the support. These ions form an ideal precursor to very small clusters of a few gold atoms upon reduction. The resulting gold clusters exhibit a very high intrinsic activity in the hydrogenation of 1,3-butadiene, which is at least one order of magnitude higher than that of the nanometre-sized gold particles in the non-leached parent catalyst. These findings point to a very strong structure sensitivity of the gold-catalyzed hydrogenation of dienes.

  20. Influence of Structure and Charge State on the Mechanism of CO Oxidation on Gold Clusters

    Science.gov (United States)

    Johnson, Grant; Burgel, Christian; Reilly, Nelly; Mitric, Roland; Kimble, Michele; Tyo, Eric; Castleman, A. W.; Bonacic-Koutecky, Vlasta

    2008-05-01

    Gas-phase reactivity experiments and high level theoretical calculations have been employed to study the interaction of both positively and negatively charged gold oxide clusters with carbon monoxide (CO). We demonstrate that for negatively charged clusters CO is oxidized to CO2 by an Eley-Ridel-like (ER-) mechanism involving the attack of CO on oxygen rather than gold. In contrast, for positively charged clusters, the oxidation reaction may also occur by a Langmuir-Hinshelwood-like (LH-) mechanism involving the initial binding of CO to a gold atom followed by subsequent migration to an oxygen site. The LH mechanism is made possible through the large energy gain associated with the adsorption of two CO molecules onto cationic gold clusters. Structure-reactivity relationships are also established which demonstrate that terminally bound oxygen atoms are the most active sites for CO oxidation. Bridge bonded oxygen atoms and molecularly bound O2 units are shown to be inert. We also establish an inverse relationship between the binding energy of CO to gold clusters and the energy of the clusters lowest unoccupied molecular orbital (LUMO).

  1. Composition dependent selectivity in the coadsorption of H2O and CO on pure and binary silver-gold clusters

    Science.gov (United States)

    Fleischer, Irene; Popolan, Denisia M.; Krstić, Marjan; Bonačić-Koutecký, Vlasta; Bernhardt, Thorsten M.

    2013-04-01

    Small cationic gold clusters exhibit a strong affinity toward carbon monoxide. This prevents the coadsorption of water which would be the first step of a catalytic water gas shift chemistry on these clusters. In a gas phase ion trap experiment with mass selected AgnAum+ it was however possible to demonstrate that the replacement of gold by silver atoms in triatomic cluster ions liberates sites for H2O adsorption. The resulting observed coadsorption effect occurs at a cross-over in the molecular binding energies of carbon monoxide and water to these clusters determined by reaction kinetics measurements and first principles calculations.

  2. Cation-Cation Complexes of Pentavalent Uranyl: From Disproportionation Intermediates to Stable Clusters

    Energy Technology Data Exchange (ETDEWEB)

    Mougel, Victor; Horeglad, Pawel; Nocton, Gregory; Pecaut, Jacques; Mazzanti, Marinella [CEA, INAC, SCIB, Laboratoire de Reconnaissance Ionique et Chimie de Coordination, CEA-Grenoble, 38054 GRENOBLE, Cedex 09 (France)

    2010-07-01

    Three new cation cation complexes of pentavalent uranyl, stable with respect to the disproportionation reaction, have been prepared from the reaction of the precursor [(UO{sub 2}py{sub 5})-(KI{sub 2}py{sub 2})]{sub n} (1) with the Schiff base ligands salen{sup 2-}, acacen{sup 2-}, and salophen{sup 2-} (H{sub 2}salen N, N'-ethylene-bis(salicylidene-imine), H{sub 2}acacen=-N, N'-ethylenebis(acetylacetone-imine), H{sub 2}salophen=N, N'-phenylene-bis(salicylidene-imine)). The preparation of stable complexes requires a careful choice of counter ions and reaction conditions. Notably the reaction of 1 with salophen{sup 2-} in pyridine leads to immediate disproportionation, but in the presence of [18]crown-6 ([18]C-6) a stable complex forms. The solid-state structure of the four tetra-nuclear complexes ([UO{sub 2}-(acacen)]{sub 4}[{mu}{sub 8}-]{sub 2}[K([18]C-6)(py)]{sub 2}) (3) and ([UO{sub 2}(acacen)](4)[{mu}{sub 8}-]).2[K([222])(py)] (4) ([UO{sub 2}(salophen)](4)[{mu}{sub 8}-K]{sub 2}[mu(5)-KI]{sub 2}[(K([18]C-6)]).2 [K([18]C-6)-(thf){sub 2}].2I (5), and ([UO{sub 2}(salen)(4)][{mu}{sub 8}-Rb]{sub 2}[Rb([18]C-6)]{sub 2}) (9) ([222] = [222]cryptand, py =pyridine), presenting a T-shaped cation cation interaction has been determined by X-ray crystallographic studies. NMR spectroscopic and UV/Vis studies show that the tetra-nuclear structure is maintained in pyridine solution for the salen and acacen complexes. Stable mononuclear complexes of pentavalent uranyl are also obtained by reduction of the hexavalent uranyl Schiff base complexes with cobaltocene in pyridine in the absence of coordinating cations. The reactivity of the complex [U{sup V}O{sub 2}(salen)(py)][Cp*{sub 2}Co] with different alkali ions demonstrates the crucial effect of coordinating cations on the stability of cation cation complexes. The nature of the cation plays a key role in the preparation of stable cation cation complexes. Stable tetra-nuclear complexes form in the presence of K

  3. A theoretical study on interaction of proline with gold cluster

    Indian Academy of Sciences (India)

    with Au3 (Pakiari and Jamshidi 2007) and interaction of. ∗. Author for correspondence (harjinder.singh@iiit.ac.in) small gold clusters with xDNA base pairs (Sharma et al. 2009) have motivated us to carry out a theoretical study on interaction of proline with gold nanoparticles. Proline is unique among the natural amino acids ...

  4. GOLD CLUSTER LABELS AND RELATED TECHNOLOGIES IN MOLECULAR MORPHOLOGY.

    Energy Technology Data Exchange (ETDEWEB)

    HAINFELD,J.F.; POWELL,R.D.

    2004-02-04

    Although intensely colored, even the largest colloidal gold particles are not, on their own, sufficiently colored for routine use as a light microscopy stain: only with very abundant antigens or with specialized illumination methods can bound gold be seen. Colloidal gold probes were developed primarily as markers for electron microscopy, for which their very high electron density and selectivity for narrow size distributions when prepared in different ways rendered them highly suited. The widespread use of gold labeling for light microscopy was made possible by the introduction of autometallographic enhancement methods. In these processes, the bound gold particles are exposed to a solution containing metal ions and a reducing agent; they catalyze the reduction of the ions, resulting in the deposition of additional metal selectively onto the particles. On the molecular level, the gold particles are enlarged up to 30-100 nm in diameter; on the macroscale level, this results in the formation of a dark stain in regions containing bound gold particles, greatly increasing visibility and contrast. The applications of colloidal gold have been described elsewhere in this chapter, we will focus on the use of covalently linked cluster complexes of gold and other metals. A gold cluster complex is a discrete molecular coordination compound comprising a central core, or ''cluster'' of electron-dense metal atoms, ligated by a shell of small organic molecules (ligands), which are linked to the metal atoms on the surface of the core. This structure gives clusters several important advantages as labels. The capping of the metal surface by ligands prevents non-specific binding to cell and tissue components, which can occur with colloidal gold. Cluster compounds are more stable and may be used under a wider range of conditions. Unlike colloidal gold, clusters do not require additional macromolecules such as bovine serum albumin or polyethylene glycol for

  5. A grand unified model for liganded gold clusters

    Science.gov (United States)

    Xu, Wen Wu; Zhu, Beien; Zeng, Xiao Cheng; Gao, Yi

    2016-12-01

    A grand unified model (GUM) is developed to achieve fundamental understanding of rich structures of all 71 liganded gold clusters reported to date. Inspired by the quark model by which composite particles (for example, protons and neutrons) are formed by combining three quarks (or flavours), here gold atoms are assigned three `flavours' (namely, bottom, middle and top) to represent three possible valence states. The `composite particles' in GUM are categorized into two groups: variants of triangular elementary block Au3(2e) and tetrahedral elementary block Au4(2e), all satisfying the duet rule (2e) of the valence shell, akin to the octet rule in general chemistry. The elementary blocks, when packed together, form the cores of liganded gold clusters. With the GUM, structures of 71 liganded gold clusters and their growth mechanism can be deciphered altogether. Although GUM is a predictive heuristic and may not be necessarily reflective of the actual electronic structure, several highly stable liganded gold clusters are predicted, thereby offering GUM-guided synthesis of liganded gold clusters by design.

  6. Structural properties of gold clusters at different temperatures

    CSIR Research Space (South Africa)

    Mahladisa, MA

    2005-09-01

    Full Text Available A series of gold clusters consisting of aggregates of from 13 to 147 atoms was studied using the Sutton-Chen type many-body potential in molecular dynamics simulations. The properties of these clusters at temperatures from 10 K to 1000 K were...

  7. Fluorescent Thiol-Derivatized Gold Clusters Embedded in Polymers

    Directory of Open Access Journals (Sweden)

    G. Carotenuto

    2013-01-01

    Full Text Available Owing to aurophilic interactions, linear and/or planar Au(I-thiolate molecules spontaneously aggregate, leading to molecular gold clusters passivated by a thiolate monolayer coating. Differently from the thiolate precursors, such cluster compounds show very intensive visible fluorescence characteristics that can be tuned by alloying the gold clusters with silver atoms or by conjugating the electronic structure of the metallic core with unsaturated electronic structures in the organic ligand through the sulphur atom. Here, the photoluminescence features of some examples of these systems are shortly described.

  8. Observing the real time formation of phosphine-ligated gold clusters by electrospray ionization mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Ligare, Marshall R.; Johnson, Grant E.; Laskin, Julia

    2017-01-01

    Early stages of the reduction and nucleation of solution-phase gold clusters are largely unknown. This is due, in part, to the high reaction rates and the complexity of the cluster synthesis process. Through the addition of a diphosphine ligand, 1-4,Bis(diphenylphosphino)butane (L4) to the gold precursor, chloro(triphenylphosphine) gold(I) (Au(PPh3)Cl), in methanol organometallic complexes of the type, [Au(L4)x(L4O)y(PPh3)z]+, are formed. These complexes lower the rate of reduction so that the reaction can be directly monitored from 1 min to over an hour using on-line electrospray ionization mass spectrometry (ESI-MS). Our results indicate that the formation of Au8(L4)42+, Au9(L4)4H2+ and Au10(L4)52+ cationic clusters occurs through different reaction pathways that may be kinetically controlled either through the reducing agent concentration or the extent of oxidation of L4. Through comparison of selected ion chronograms our results indicate that Au2(L4)2H+ may be an intermediate in the formation of Au8(L4)42+and Au10(L4)52+ while a variety of chlorinated clusters are involved in the formation of Au9(L4)4H2+. Additionally, high-resolution mass spectrometry was employed to identify 53 gold containing species produced under highly oxidative conditions. New intermediate species are identified which help understand how different gold cluster nuclearities can be stabilized during the growth process.

  9. Structures of 38-atom gold-platinum nanoalloy clusters

    Energy Technology Data Exchange (ETDEWEB)

    Ong, Yee Pin; Yoon, Tiem Leong [School of Physics, Universiti Sains Malaysia, 11800 USM, Penang (Malaysia); Lim, Thong Leng [Faculty of Engineering and Technology, Multimedia University, Melaka Campus, 75450 Melaka (Malaysia)

    2015-04-24

    Bimetallic nanoclusters, such as gold-platinum nanoclusters, are nanomaterials promising wide range of applications. We perform a numerical study of 38-atom gold-platinum nanoalloy clusters, Au{sub n}Pt{sub 38−n} (0 ≤ n ≤ 38), to elucidate the geometrical structures of these clusters. The lowest-energy structures of these bimetallic nanoclusters at the semi-empirical level are obtained via a global-minimum search algorithm known as parallel tempering multi-canonical basin hopping plus genetic algorithm (PTMBHGA), in which empirical Gupta many-body potential is used to describe the inter-atomic interactions among the constituent atoms. The structures of gold-platinum nanoalloy clusters are predicted to be core-shell segregated nanoclusters. Gold atoms are observed to preferentially occupy the surface of the clusters, while platinum atoms tend to occupy the core due to the slightly smaller atomic radius of platinum as compared to gold’s. The evolution of the geometrical structure of 38-atom Au-Pt clusters displays striking similarity with that of 38-atom Au-Cu nanoalloy clusters as reported in the literature.

  10. Small gold clusters on graphene, their mobility and clustering: a DFT study

    International Nuclear Information System (INIS)

    Amft, Martin; Sanyal, Biplab; Eriksson, Olle; Skorodumova, Natalia V

    2011-01-01

    Motivated by the experimentally observed high mobility of gold atoms on graphene and their tendency to form nanometer-sized clusters, we present a density functional theory study of the ground state structures of small gold clusters on graphene, their mobility and clustering. Our detailed analysis of the electronic structures identifies the opportunity to form strong gold-gold bonds and the graphene-mediated interaction of the pre-adsorbed fragments as the driving forces behind gold's tendency to aggregate on graphene. While clusters containing up to three gold atoms have one unambiguous ground state structure, both gas phase isomers of a cluster with four gold atoms can be found on graphene. In the gas phase the diamond-shaped Au 4 D cluster is the ground state structure, whereas the Y-shaped Au 4 Y becomes the actual ground state when adsorbed on graphene. As we show, both clusters can be produced on graphene by two distinct clustering processes. We also studied in detail the stepwise formation of a gold dimer out of two pre-adsorbed adatoms, as well as the formation of Au 3 . All reactions are exothermic and no further activation barriers, apart from the diffusion barriers, were found. The diffusion barriers of all studied clusters range from 4 to 36 meV only, and are substantially exceeded by the adsorption energies of - 0.1 to - 0.59 eV. This explains the high mobility of Au 1-4 on graphene along the C-C bonds.

  11. Ligand-protected gold clusters: the structure, synthesis and applications

    International Nuclear Information System (INIS)

    Pichugina, D A; Kuz'menko, N E; Shestakov, A F

    2015-01-01

    Modern concepts of the structure and properties of atomic gold clusters protected by thiolate, selenolate, phosphine and phenylacetylene ligands are analyzed. Within the framework of the superatom theory, the 'divide and protect' approach and the structure rule, the stability and composition of a cluster are determined by the structure of the cluster core, the type of ligands and the total number of valence electrons. Methods of selective synthesis of gold clusters in solution and on the surface of inorganic composites based, in particular, on the reaction of Au n with RS, RSe, PhC≡C, Hal ligands or functional groups of proteins, on stabilization of clusters in cavities of the α-, β and γ-cyclodextrin molecules (Au 15 and Au 25 ) and on anchorage to a support surface (Au 25 /SiO 2 , Au 20 /C, Au 10 /FeO x ) are reviewed. Problems in this field are also discussed. Among the methods for cluster structure prediction, particular attention is given to the theoretical approaches based on the density functional theory (DFT). The structures of a number of synthesized clusters are described using the results obtained by X-ray diffraction analysis and DFT calculations. A possible mechanism of formation of the SR(AuSR) n 'staple' units in the cluster shell is proposed. The structure and properties of bimetallic clusters M x Au n L m (M=Pd, Pt, Ag, Cu) are discussed. The Pd or Pt atom is located at the centre of the cluster, whereas Ag and Cu atoms form bimetallic compounds in which the heteroatom is located on the surface of the cluster core or in the 'staple' units. The optical properties, fluorescence and luminescence of ligand-protected gold clusters originate from the quantum effects of the Au atoms in the cluster core and in the oligomeric SR(AuSR) x units in the cluster shell. Homogeneous and heterogeneous reactions catalyzed by atomic gold clusters are discussed in the context of the reaction mechanism and the nature of the active

  12. Ligand-protected gold clusters: the structure, synthesis and applications

    Science.gov (United States)

    Pichugina, D. A.; Kuz'menko, N. E.; Shestakov, A. F.

    2015-11-01

    Modern concepts of the structure and properties of atomic gold clusters protected by thiolate, selenolate, phosphine and phenylacetylene ligands are analyzed. Within the framework of the superatom theory, the 'divide and protect' approach and the structure rule, the stability and composition of a cluster are determined by the structure of the cluster core, the type of ligands and the total number of valence electrons. Methods of selective synthesis of gold clusters in solution and on the surface of inorganic composites based, in particular, on the reaction of Aun with RS, RSe, PhC≡C, Hal ligands or functional groups of proteins, on stabilization of clusters in cavities of the α-, β and γ-cyclodextrin molecules (Au15 and Au25) and on anchorage to a support surface (Au25/SiO2, Au20/C, Au10/FeOx) are reviewed. Problems in this field are also discussed. Among the methods for cluster structure prediction, particular attention is given to the theoretical approaches based on the density functional theory (DFT). The structures of a number of synthesized clusters are described using the results obtained by X-ray diffraction analysis and DFT calculations. A possible mechanism of formation of the SR(AuSR)n 'staple' units in the cluster shell is proposed. The structure and properties of bimetallic clusters MxAunLm (M=Pd, Pt, Ag, Cu) are discussed. The Pd or Pt atom is located at the centre of the cluster, whereas Ag and Cu atoms form bimetallic compounds in which the heteroatom is located on the surface of the cluster core or in the 'staple' units. The optical properties, fluorescence and luminescence of ligand-protected gold clusters originate from the quantum effects of the Au atoms in the cluster core and in the oligomeric SR(AuSR)x units in the cluster shell. Homogeneous and heterogeneous reactions catalyzed by atomic gold clusters are discussed in the context of the reaction mechanism and the nature of the active sites. The bibliography includes 345 references.

  13. How the cation-cation π-π stacking occurs: A theoretical investigation into ionic clusters of imidazolium.

    Science.gov (United States)

    Gao, Wei; Tian, Yong; Xuan, Xiaopeng

    2015-07-01

    The cation-cation π-π stacking is uncommon but it is essential for the understanding of some supramolecular structures. We explore theoretically the nature of non-covalent interaction occurring in the stacked structure within modeled clusters of 1,3-dimethylimidazolium and halide. The evidences of the energy decomposition analysis (EDA) and reduced density gradient (RDG) approach are different from those of common π-π interaction. Isosurfaces with RDG also illustrate the strength of the titled π-π interaction and their region. Additionally, we find that the occurrence of this interaction is attributed to a few C-H···X interactions, as depicted using atom in molecule (AIM) method. This work presents a clear picture of the typical cation-cation π-π interaction and can serve to advance the understanding of this uncommon interaction. Copyright © 2015 Elsevier Inc. All rights reserved.

  14. Density functional study of carbon monoxide adsorption on small cationic, neutral, and anionic aluminum nitride clusters

    Science.gov (United States)

    Guo, Ling

    CO adsorption on small cationic, neutral, and anionic (AlN)n (n = 1-6) clusters has been investigated using density functional theory in the generalized gradient approximation. Among various possible CO adsorption sites, an N on-top (onefold coordinated) site is found to be the most favorable one, irrespective of the charge state of the clusters. The adsorption energies of CO on the anionic (AlN)nCO (n = 2-4) clusters are greater than those on the neutral and cationic complexes. The adsorption energies on the cationic and neutral complexes reflect the odd-even oscillations, and the adsorption energies of CO on the cationic (AlN)nCO (n = 5, 6) clusters are greater than those on the neutral and anionic complexes. The adsorption energies for the different charge states decrease with increasing cluster size.

  15. The nature and role of the gold-krypton interactions in small neutral gold clusters.

    Science.gov (United States)

    Mancera, Luis A; Benoit, David M

    2015-03-26

    We investigate the nature and role of krypton embedding in small neutral gold clusters. For some of these clusters, we observe a particular site-dependent character of the Kr binding that does not completely follow the criterion of binding at low-coordinated sites, widely accepted for interaction of a noble gas with closed-shell metal systems such as metal surfaces. We aim at understanding the effect of low dimensionality and open-shell electronic structure of the odd-numbered clusters on the noble gas-metal cluster interaction. First, we investigate the role of attractive and repulsive forces, and the frontier molecular orbitals. Second, we investigate the Au-Kr interaction in terms of reactivity and bonding character. We use a reactivity index derived from Fukui formalism, and criteria provided by the electron localization function (ELF), in order to classify the type of bonding. We carry out this study on the minimum energy structures of neutral gold clusters, as obtained using pseudo potential plane-wave density functional theory (DFT). A model is proposed that includes the effect of attractive electrostatic, van der Waals and repulsive forces, together with effects originating from orbital overlap. This satisfactorily explains minimum configurations of the noble gas-gold cluster systems, the site preference of the noble gas atoms, and changes in electronic properties.

  16. Quantum chemical study of the interaction of elemental Hg with small neutral, anionic and cationic Aun (n = 1–6) clusters

    International Nuclear Information System (INIS)

    Siddiqui, Shamoon Ahmad; Bouarissa, Nadir; Rasheed, Tabish; Al-Assiri, M.S.

    2013-01-01

    Graphical abstract: Binding energies as a function of cluster size for Au n Hg, Au n Hg + and Au n Hg − complexes. Highlights: ► Hg adsorption of neutral and charged Au n (n = 1–6) clusters has been discussed. ► Size and charged state of cluster significantly affect the Hg adsorption. ► Transfer of electron mainly found from s orbital of Hg to s orbital of Au. - Abstract: Adsorption of elemental mercury (Hg) on small neutral, cationic and anionic gold clusters (Au n , n = 1–6) has been studied by using the density functional theory (DFT). Results of this investigation show that frontier molecular orbital theory is a useful tool to predict the selectivity of Hg adsorption. It is found that adsorption of Hg on neutral, cationic and anionic Au n (n = 1–6) clusters are thermodynamically favorable. The binding energies of Hg on the cationic Au n clusters are greater than those on the neutral and anionic clusters. Natural bond orbital (NBO) analysis indicates that the flow of electrons in the neutral and charged clusters is mainly due to the s orbitals of Hg and Au. Results of NBO analysis also indicate that the binding energy of Hg with Au n clusters is directly proportional to the charge transfer, i.e. greater is the charge transfer, higher is the binding energy

  17. Molecular dynamics simulation of gold cluster growth during sputter deposition

    Energy Technology Data Exchange (ETDEWEB)

    Abraham, J. W., E-mail: abraham@theo-physik.uni-kiel.de; Bonitz, M., E-mail: bonitz@theo-physik.uni-kiel.de [Institut für Theoretische Physik und Astrophysik, Christian-Albrechts-Universität zu Kiel, Leibnizstraße 15, D-24098 Kiel (Germany); Strunskus, T.; Faupel, F. [Institut für Materialwissenschaft, Lehrstuhl für Materialverbunde, Christian-Albrechts-Universität zu Kiel, Kaiserstraße 2, D-24143 Kiel (Germany)

    2016-05-14

    We present a molecular dynamics simulation scheme that we apply to study the time evolution of the self-organized growth process of metal cluster assemblies formed by sputter-deposited gold atoms on a planar surface. The simulation model incorporates the characteristics of the plasma-assisted deposition process and allows for an investigation over a wide range of deposition parameters. It is used to obtain data for the cluster properties which can directly be compared with recently published experimental data for gold on polystyrene [M. Schwartzkopf et al., ACS Appl. Mater. Interfaces 7, 13547 (2015)]. While good agreement is found between the two, the simulations additionally provide valuable time-dependent real-space data of the surface morphology, some of whose details are hidden in the reciprocal-space scattering images that were used for the experimental analysis.

  18. Chemically induced magnetism in atomically precise gold clusters.

    Science.gov (United States)

    Krishna, Katla Sai; Tarakeshwar, Pilarisetty; Mujica, Vladimiro; Kumar, Challa S S R

    2014-03-12

    Comparative theoretical and experimental investigations are reported into chemically induced magnetism in atomically-precise, ligand-stabilized gold clusters Au25 , Au38 and Au55 . The results indicate that [Au25 (PPh3 )10 (SC12 H25 )5 Cl2 ](2+) and Au38 (SC12 H25 )24 are diamagnetic, Au25 (SC2 H4 Ph)18 is paramagnetic, and Au55 (PPh3 )12 Cl6 , is ferromagnetic at room temperature. Understanding the magnetic properties resulting from quantum size effects in such atomically precise gold clusters could lead to new fundamental discoveries and applications. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Impact of slow gold clusters on various solids

    International Nuclear Information System (INIS)

    Benguerba, M.; Brunelle, A.; Della-Negra, S.; Depauw, J.; Joret, H.; Beyec, Y. Le; Schweikert, E.A.; Assayag, G.B.; Sudraud, P.

    1991-01-01

    A liquid metal ion source has been installed on a pulsed ion gun. The time of flight (TOF) spectra of the pulsed beam were recorded. With the gold source several cluster ions (up to 10 atoms in the cluster) and doubly charged ions were identified in the ion beam TOF spectra. With a second pulsation, single cluster ions can be selected as projectiles for secondary ion TOF mass spectrometry. The secondary ion emission induced by cluster impact from a variety of targets (organic, CsI, metallic) was studied. A large enhancement of yield is observed by comparison to single atomic ion impact (e.g., a factor of 30 between Au 3 + and Au + ). The secondary ion yields increase nonlinearly with the number of constituents in the cluster. A comparison with other types of clusters and also fission fragments of 252 Cf has been performed. The rate of secondary emission stimulated by cluster is similar to the secondary ion yield induced by fission fragments. (author) 47 refs., 18 figs., 5 tabs

  20. Binding motif of terminal alkynes on gold clusters.

    Science.gov (United States)

    Maity, Prasenjit; Takano, Shinjiro; Yamazoe, Seiji; Wakabayashi, Tomonari; Tsukuda, Tatsuya

    2013-06-26

    Gold clusters protected by terminal alkynes (1-octyne (OC-H), phenylacetylene (PA-H) and 9-ethynyl-phenanthrene (EPT-H)) were prepared by the ligand exchange of small (diameter alkynes on Au clusters was investigated using various spectroscopic methods. FTIR and Raman spectroscopy revealed that terminal hydrogen is lost during the ligand exchange and that the C≡C bond of the alkynyl group is weakened upon attachment to the Au clusters. Acidification of the water phase after the ligand exchange indicated that the ligation of alkynyl groups to the Au clusters proceeds via deprotonation of the alkynes. A series of precisely defined Au clusters, Au34(PA)16, Au54(PA)26, Au30(EPT)13, Au35(EPT)18, and Au(41-43)(EPT)(21-23), were synthesized and characterized in detail to obtain further insight into the interfacial structures. Careful mass analysis confirmed the ligation of the alkynes in the dehydrogenated form. An upright configuration of the alkynes on Au clusters was suggested from the Au to alkyne ratios and photoluminescence from the excimer of the EPT ligands. EXAFS analysis implied that the alkynyl carbon is bound to bridged or hollow sites on the cluster surface.

  1. Cation-Dependent Gold Recovery with α-Cyclodextrin Facilitated by Second-Sphere Coordination.

    Science.gov (United States)

    Liu, Zhichang; Samanta, Avik; Lei, Juying; Sun, Junling; Wang, Yuping; Stoddart, J Fraser

    2016-09-14

    Herein, we report an alkali metal cation-dependent approach to gold recovery, facilitated by second-sphere coordination with eco-friendly α-cyclodextrin (α-CD). Upon mixing eight salts composed of Na(+), K(+), Rb(+), or Cs(+) cations and [AuX4](-) (X = Cl/Br) anions with α-, β-, or γ-CD in water, co-precipitates form selectively from the three (out of 24) aqueous solutions containing α-CD with KAuBr4, RbAuBr4, and CsAuBr4, from which the combination of α-CD and KAuBr4 affords the highest yield. Single-crystal X-ray analyses reveal that in 20 of the 24 adducts CD and [AuX4](-) anions form 2:1 sandwich-type second-sphere adducts driven partially by [C-H···X-Au] interactions between [AuX4](-) anions and the primary faces of two neighboring CDs. In the adduct formed between α-CD and KAuBr4, a [K(OH2)6](+) cation is encapsulated inside the cavity between the secondary faces of two α-CDs, leading to highly efficient precipitation owing to the formation of a cation/anion alternating ion wire residing inside a continuous α-CD nanotube. By contrast, in the other 19 adducts, the cations are coordinated by OH groups and glucopyranosyl ring O atoms in CDs. The strong coordination of Rb(+) and Cs(+) cations by these ligands, in conjunction with the stereoelectronically favorable binding of [AuBr4](-) anions with two α-CDs, facilitates the co-precipitation of the two adducts formed between α-CD with RbAuBr4 and CsAuBr4. In order to develop an efficient process for green gold recovery, the co-precipitation yield of α-CD and KAuBr4 has been optimized regarding both the temperature and the molar ratio of α-CD to KAuBr4.

  2. Photoemission on gold-55-clusters derived from gold-phosphine AuP(C6H5)3Cl

    International Nuclear Information System (INIS)

    Quinten, M.; Sander, I.; Steiner, P.; Kreibig, U.; Fauth, K.; Schmid, G.

    1991-01-01

    We measured XPS and UPS spectra of gold clusters with 55 atoms, embedded in an electrically isolating phosphine matrix, and of gold-phosphine, from which the clusters were chemically derived. Compared to the spectra of bulk gold the valence band spectrum and the core level spectra of the clusters showed shifts of the peaks and the fermi level to higher binding energies. The shift of the peaks could qualitatively be interpreted by a final state effect. We succeeded in a separation of bulk and surface contributions to the core level spectra and in a reasonable quantitative analysis of the valence band spectrum of the clusters. The Au 4f core level spectrum of gold-phosphine showed two peaks at 1.5 eV higher binding energies than the corresponding peaks of the clusters. (orig.)

  3. Water-induced adsorption of carbon monoxide and oxygen on the gold dimer cation.

    Science.gov (United States)

    Ito, Tomonori; Patwari, G Naresh; Arakawa, Masashi; Terasaki, Akira

    2014-09-18

    It is demonstrated, using tandem mass spectrometry and ion trap, that preadsorption of a H2O molecule on the gold dimer cation, Au2(+), enhances adsorption of CO and O2 molecules, which is otherwise inert toward these molecules. The rate of adsorption of CO on Au2(H2O)(+) was found to be higher by 2 orders of magnitude relative to bare Au2(+). The enhancement of the CO adsorption rate is due to the presence of a reaction channel, which cleaves the Au-Au bond, leading to the formation of Au(H2O)(CO)(+). Such an observation can be attributed to weakening of the Au-Au bond upon adsorption of a water molecule. Further, it was also observed that preadsorption of H2O leads to dramatic enhancement of O2 adsorption on the Au2(+) ion, which can be attributed to the changes in the electron density following water adsorption.

  4. Temperature effects on the stability of gold nanoparticles in the presence of a cationic thermoresponsive copolymer

    Energy Technology Data Exchange (ETDEWEB)

    Pamies, Ramón [Technical University of Cartagena, Department of Material Engineering and Manufacturing (Spain); Zhu, Kaizheng [University of Oslo, Department of Chemistry (Norway); Kjøniksen, Anna-Lena, E-mail: anna.l.kjoniksen@hiof.no [Østfold University College, Faculty of Engineering (Norway); Nyström, Bo [University of Oslo, Department of Chemistry (Norway)

    2016-11-15

    New hybrid complexes composed by a thermoresponsive copolymer and gold nanoparticles (R{sub h} = 22 nm) have been characterized by dynamic light scattering (DLS) and UV-visible spectroscopy. A cationic thermoresponsive triblock copolymer, methoxy-poly(ethylene glycol)-block-poly(N-isopropylacrylamide)-block-poly((3-acrylamidopropyl) trimethyl ammonium chloride), abbreviated as MPEG-b-PNIPAAM-b-PN(+), has been synthesized by atom transfer radical polymerization (ATRP). We have evaluated the thermal response at low concentrations of this triblock copolymer in bulk solution and the effect of concentration on the interaction between this thermosensitive copolymer and the gold nanoparticles (AuNPs) to form new hybrid complexes (60–1000 nm) at different temperatures. The thermosensitive nature of the copolymer causes both aggregation and contraction of the aggregates at elevated temperatures. The AuNPs were found to be separately embedded in the hybrid complexes. Interestingly, the AuNPs prevent macroscopic phase separation of the system at high temperatures.

  5. Cationic and neutral copper(I) iodide cluster MOFs derived from ...

    Indian Academy of Sciences (India)

    Ashok Yadav

    These reactions yielded two new cluster-MOFs 2 and 3. While the ..... (a) Ortep plots at 50% ellipsoid probabilities for the cationic segments of 2; (b) View of the. 3D-MOF assembly of 2 ... identical emission colour of 2 at 298 K and 77 K under the. UV-lamp. .... C 2013 A multi-metal-cluster MOF with Cu4I4 and. Cu6S6 as ...

  6. Ligand induced structural isomerism in phosphine coordinated gold clusters revealed by ion mobility mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Ligare, Marshall R.; Baker, Erin M.; Laskin, Julia; Johnson, Grant E.

    2017-01-01

    Structural isomerism in ligated gold clusters is revealed using electrospray ionization ion mobility spectrometry mass spectrometry. Phosphine ligated Au8 clusters are shown to adopt more “extended” type structures with increasing exchange of methyldiphenylphosphine (MePPh2) for triphenylphosphine (PPh3). These ligand-dependant structure-property relationships are critical to applications of clusters in catalysis.

  7. Metal cluster cation reactions: Carbon monoxide association to Cu + n ions

    Science.gov (United States)

    Leuchtner, R. E.; Harms, A. C.; Castleman, A. W., Jr.

    1990-06-01

    Copper cluster cations (Cu+n,n=1-14) were produced in a laser vaporization/flow tube apparatus and equilibrated to room temperature. The association rate constants of carbon monoxide onto these ions were measured; low-pressure, termolecular behavior was observed for the smaller species while for clusters greater than Cu+7, the longer lifetimes due to the increased number of degrees of freedom leads to pressure independence (>0.3 Torr) of the effective bimolecular rates. Unimolecular decay theory (RRKM) is used to explain the overall trend and when intrinsic surface site reactivity is taken into account, excellent agreement with measured reactivity is obtained.

  8. Spectroscopy of electronic transitions in Polycyclic Aromatic Hydrocarbon cations and their clusters

    International Nuclear Information System (INIS)

    Friha, Hela

    2012-01-01

    This thesis is an experimental study of the electronic spectroscopy of cations of Polycyclic Aromatic Hydrocarbons (PAHs) and their aggregates in conditions close to those of the interstellar medium (ISM), i.e. cold and totally isolated in the gas phase. It is related to the astrophysical context of the interstellar medium (ISM), in particular on the question of the possible link between interstellar PAHs and Diffuse Interstellar Bands (DIBs). The purpose of this thesis is to provide laboratory spectra which can be directly compared to the spectra of DIBs. Indeed these bands are the oldest spectroscopy riddle in astrophysics which remained unanswered for nearly 100 years and whose key is still looked for. A special attention is given to the methylated derivatives of PAHs species detected in many interstellar environments, cationic PAH dimers (the simplest PAH clusters). These clusters have been proposed as a model of the very small grains, which contribute to the formation of interstellar PAHs and whose chemical composition remains uncertain. This thesis has been mainly devoted to the determination of the electronic spectra of naphthalene cation monomer (Np + ) and its methylated derivative (2-MeN p + ), as well as the associated homogeneous dimers. The experimental method used is based on the photodissociation of van der Waals complexes PAH + m -Ar n (argon atoms spectators), prepared by UV laser photoionization in a supersonic jet. This technique combines different experimental tools, namely: molecular beam mass spectrometry and laser spectroscopy as well as physical tools such as the handling of clusters VdW PAH + m -Ar n , the detection of photo-fragments, the measurement of photodissociation efficiency. The identification of the fragments by the photodissociation of VdW clusters allowed us to determine the different possible fragmentation channels and especially to obtain the spectra the charge resonance transition and the first allowed transition to locally

  9. Density functional study of structural and electronic properties of bimetallic silver-gold clusters: Comparison with pure gold and silver clusters

    Science.gov (United States)

    Bonacic-Koutecky, Vlasta; Burda, Jaroslav; Mitric, Roland; Ge, Maofa; Zampella, Giuseppe; Fantucci, Piercarlo

    2002-08-01

    Bimetallic silver-gold clusters offer an excellent opportunity to study changes in metallic versus "ionic" properties involving charge transfer as a function of the size and the composition, particularly when compared to pure silver and gold clusters. We have determined structures, ionization potentials, and vertical detachment energies for neutral and charged bimetallic AgmAun 3[less-than-or-equal](m+n)[less-than-or-equal]5 clusters. Calculated VDE values compare well with available experimental data. In the stable structures of these clusters Au atoms assume positions which favor the charge transfer from Ag atoms. Heteronuclear bonding is usually preferred to homonuclear bonding in clusters with equal numbers of hetero atoms. In fact, stable structures of neutral Ag2Au2, Ag3Au3, and Ag4Au4 clusters are characterized by the maximum number of hetero bonds and peripheral positions of Au atoms. Bimetallic tetramer as well as hexamer are planar and have common structural properties with corresponding one-component systems, while Ag4Au4 and Ag8 have 3D forms in contrast to Au8 which assumes planar structure. At the density functional level of theory we have shown that this is due to participation of d electrons in bonding of pure Aun clusters while s electrons dominate bonding in pure Agm as well as in bimetallic clusters. In fact, Aun clusters remain planar for larger sizes than Agm and AgnAun clusters. Segregation between two components in bimetallic systems is not favorable, as shown in the example of Ag5Au5 cluster. We have found that the structures of bimetallic clusters with 20 atoms Ag10Au10 and Ag12Au8 are characterized by negatively charged Au subunits embedded in Ag environment. In the latter case, the shape of Au8 is related to a pentagonal bipyramid capped by one atom and contains three exposed negatively charged Au atoms. They might be suitable for activating reactions relevant to catalysis. According to our findings the charge transfer in bimetallic

  10. Scanning probe microscopy investigation of gold clusters deposited on atomically flat substrates

    International Nuclear Information System (INIS)

    Vandamme, N; Janssens, E; Vanhoutte, F; Lievens, P; Haesendonck, C van

    2003-01-01

    We systematically studied the influence of the substrate on the shape, mobility, and stability of deposited gold clusters. The Au n clusters were produced in a laser vaporization source and deposited with low kinetic energy (∼0.4 eV/atom) on atomically flat substrates (graphite, mica, and gold and silver films on mica) under UHV conditions. Their size distribution is probed with time-of-flight mass spectrometry and ranges from dimers to several hundreds of atoms. Scanning probe microscopy is used to characterize the deposited clusters and the formation of islands by cluster aggregation. On all substrates, Au n islands can be clearly distinguished and the islands are flattened despite the small impact energy. The shape and size of the island configurations are strongly system dependent. Gold clusters deposited on Au(111) and Ag(111) films grown on mica do not aggregate, but deform due to strong cluster-substrate interactions. The clusters tend to grow epitaxially on these surfaces. On graphite and on mica, deposited clusters do diffuse and aggregate. On the graphite surface, large ramified islands are formed by juxtaposition of small islands and trapping of the clusters at the step edges. On the other hand, the diffusion of the clusters on mica results in a total coalescence of the Au n clusters into compact islands

  11. Melting behaviour of gold-platinum nanoalloy clusters by molecular dynamics simulations

    Energy Technology Data Exchange (ETDEWEB)

    Ong, Yee Pin; Yoon, Tiem Leong [School of Physics, Universiti Sains Malaysia, 11800 USM, Penang (Malaysia); Lim, Thong Leng [Faculty of Engineering and Technology, Multimedia University, Melaka Campus, 75450 Melaka (Malaysia)

    2015-04-24

    The melting behavior of bimetallic gold-platinum nanoclusters is studied by applying Brownian-type isothermal molecular dynamics (MD) simulation, a program modified from the cubic coupling scheme (CCS). The process begins with the ground-state structures obtained from global minimum search algorithm and proceeds with the investigation of the effect of temperature on the thermal properties of gold-platinum nanoalloy clusters. N-body Gupta potential has been employed in order to account for the interactions between gold and platinum atoms. The ground states of the nanoalloy clusters, which are core-shell segregated, are heated until they become thermally segregated. The detailed melting mechanism of the nanoalloy clusters is studied via this approach to provide insight into the thermal stability of the nanoalloy clusters.

  12. Pronounced cluster-size effects: gas-phase reactivity of bare vanadium cluster cations V(n)+ (n = 1-7) toward methanol.

    Science.gov (United States)

    Feyel, Sandra; Schröder, Detlef; Schwarz, Helmut

    2009-05-14

    Mass spectrometric experiments are used to examine the size-dependent interactions of bare vanadium cluster cations V(n)(+) (n = 1-7) with methanol. The reactivity patterns exhibit enormous size effects throughout the range of clusters investigated. For example, dehydrogenation of methanol to produce V(n)OC(+) is only brought about by clusters with n > or = 3. Atomic vanadium cation V(+) also is reactive, but instead of dehydrogenation of the alcohol, expulsions of either methane or a methyl radical take place. In marked contrast, the reaction efficiency of the dinuclear cluster V(2)(+) is extremely low. For the cluster cations V(n)(+) (n = 3-7), complete and efficient dehydrogenation of methanol to produce V(n)OC(+) and two hydrogen molecules prevails. DFT calculations shed light on the mechanism of the dehydrogenation of methanol by the smallest reactive cluster cation V(3)(+) and propose the occurrence of chemisorption concomitant with C-O bond cleavage rather than adsorption of an intact carbon monoxide molecule by the cluster.

  13. Anti-trypanosomal activity of cationic N-heterocyclic carbene gold(I) complexes.

    Science.gov (United States)

    Winter, Isabel; Lockhauserbäumer, Julia; Lallinger-Kube, Gertrud; Schobert, Rainer; Ersfeld, Klaus; Biersack, Bernhard

    2017-06-01

    Two gold(I) N-heterocyclic carbene complexes 1a and 1b were tested for their anti-trypanosomal activity against Trypanosoma brucei parasites. Both gold compounds exhibited excellent anti-trypanosomal activity (IC 50 =0.9-3.0nM). The effects of the gold complexes 1a and 1b on the T. b. brucei cytoskeleton were evaluated. Rapid detachment of the flagellum from the cell body occurred after treatment with the gold complexes. In addition, a quick and complete degeneration of the parasitic cytoskeleton was induced by the gold complexes, only the microtubules of the detached flagellum remained intact. Both gold compounds 1a and 1b feature selective anti-trypanosomal agents and were distinctly more active against T. b. brucei cells than against human HeLa cells. Thus, the gold complexes 1a and 1b feature promising drug candidates for the treatment of trypanosome infections such as sleeping sickness (human African Trypanosomiasis caused by Trypanosoma brucei parasites). Copyright © 2017 Elsevier B.V. All rights reserved.

  14. Photo-induced transformation process at gold clusters-semiconductor interface: Implications for the complexity of gold clusters-based photocatalysis

    Science.gov (United States)

    Liu, Siqi; Xu, Yi-Jun

    2016-03-01

    The recent thrust in utilizing atomically precise organic ligands protected gold clusters (Au clusters) as photosensitizer coupled with semiconductors for nano-catalysts has led to the claims of improved efficiency in photocatalysis. Nonetheless, the influence of photo-stability of organic ligands protected-Au clusters at the Au/semiconductor interface on the photocatalytic properties remains rather elusive. Taking Au clusters-TiO2 composites as a prototype, we for the first time demonstrate the photo-induced transformation of small molecular-like Au clusters to larger metallic Au nanoparticles under different illumination conditions, which leads to the diverse photocatalytic reaction mechanism. This transformation process undergoes a diffusion/aggregation mechanism accompanied with the onslaught of Au clusters by active oxygen species and holes resulting from photo-excited TiO2 and Au clusters. However, such Au clusters aggregation can be efficiently inhibited by tuning reaction conditions. This work would trigger rational structural design and fine condition control of organic ligands protected-metal clusters-semiconductor composites for diverse photocatalytic applications with long-term photo-stability.

  15. Controlled Clustering of Gold Nanoparticles using Solid-support for Surface-enhanced Raman Spectroscopic Probes

    International Nuclear Information System (INIS)

    Chang, Hyejin; Chae, Jinjoo; Jeong, Hong; Kang, Homan; Lee, Yoonsik

    2014-01-01

    We fabricated small clusters of gold nanoparticles by using solid-supported aggregation of gold nanoparticles. The fabricated Au nanoclusters consisting mainly of dimers showed homogeneous characteristics in cluster size and SERS intensity. The SERS enhancement of 4-ABT molecules in an effective area within 2-nm gap appeared to be approximately 10. Detachment process by ultrasonication was successively carried out in order to use the nanoclusters as SERS probes. The possibility of these clusters as SERS probe was proved in terms of signal and cluster size. Single molecule-level sensitivity of surface-enhanced Raman scattering (SERS) was known approximately fifteen years ago. Ever since there have been many different applications benefiting from the ultra-high sensitivity such as single molecule detection, chemical sensing and bio-molecular probes. Especially, SERS has drawn much attention in bio-multiplexing probes owing to its unique optical characteristics claiming extremely narrow bandwidth, high sensitivity of light signals, and non-bleaching feature

  16. Controlled Clustering of Gold Nanoparticles using Solid-support for Surface-enhanced Raman Spectroscopic Probes

    Energy Technology Data Exchange (ETDEWEB)

    Chang, Hyejin; Chae, Jinjoo; Jeong, Hong [Department of Chemistry Education, Seoul (Korea, Republic of); Kang, Homan; Lee, Yoonsik [Interdisciplinary Program in Nano-Science and Technology, Pohang (Korea, Republic of)

    2014-03-15

    We fabricated small clusters of gold nanoparticles by using solid-supported aggregation of gold nanoparticles. The fabricated Au nanoclusters consisting mainly of dimers showed homogeneous characteristics in cluster size and SERS intensity. The SERS enhancement of 4-ABT molecules in an effective area within 2-nm gap appeared to be approximately 10. Detachment process by ultrasonication was successively carried out in order to use the nanoclusters as SERS probes. The possibility of these clusters as SERS probe was proved in terms of signal and cluster size. Single molecule-level sensitivity of surface-enhanced Raman scattering (SERS) was known approximately fifteen years ago. Ever since there have been many different applications benefiting from the ultra-high sensitivity such as single molecule detection, chemical sensing and bio-molecular probes. Especially, SERS has drawn much attention in bio-multiplexing probes owing to its unique optical characteristics claiming extremely narrow bandwidth, high sensitivity of light signals, and non-bleaching feature.

  17. Self-Assembled Gold Nano-Ripple Formation by Gas Cluster Ion Beam Bombardment.

    Science.gov (United States)

    Tilakaratne, Buddhi P; Chen, Quark Y; Chu, Wei-Kan

    2017-09-08

    In this study, we used a 30 keV argon cluster ion beam bombardment to investigate the dynamic processes during nano-ripple formation on gold surfaces. Atomic force microscope analysis shows that the gold surface has maximum roughness at an incident angle of 60° from the surface normal; moreover, at this angle, and for an applied fluence of 3 × 10 16 clusters/cm², the aspect ratio of the nano-ripple pattern is in the range of ~50%. Rutherford backscattering spectrometry analysis reveals a formation of a surface gradient due to prolonged gas cluster ion bombardment, although the surface roughness remains consistent throughout the bombarded surface area. As a result, significant mass redistribution is triggered by gas cluster ion beam bombardment at room temperature. Where mass redistribution is responsible for nano-ripple formation, the surface erosion process refines the formed nano-ripple structures.

  18. Complexes of DNA bases and Watson-Crick base pairs with small neutral gold clusters.

    Science.gov (United States)

    Kryachko, E S; Remacle, F

    2005-12-08

    The nature of the DNA-gold interaction determines and differentiates the affinity of the nucleobases (adenine, thymine, guanine, and cytosine) to gold. Our preliminary computational study [Kryachko, E. S.; Remacle, F. Nano Lett. 2005, 5, 735] demonstrates that two major bonding factors govern this interaction: the anchoring, either of the Au-N or Au-O type, and the nonconventional N-H...Au hydrogen bonding. In this paper, we offer insight into the nature of nucleobase-gold interactions and provide a detailed characterization of their different facets, i.e., geometrical, energetic, and spectroscopic aspects; the gold cluster size and gold coordination effects; proton affinity; and deprotonation energy. We then investigate how the Watson-Crick DNA pairing patterns are modulated by the nucleobase-gold interaction. We do so in terms of the proton affinities and deprotonation energies of those proton acceptors and proton donors which are involved in the interbase hydrogen bondings. A variety of properties of the most stable Watson-Crick [A x T]-Au3 and [G x C]-Au3 hybridized complexes are described and compared with the isolated Watson-Crick A x T and G x C ones. It is shown that enlarging the gold cluster size to Au6 results in a rather short gold-gold bond in the Watson-Crick interbase region of the [G x C]-Au6 complex that bridges the G x C pair and thus leads to a significant strengthening of G x C pairing.

  19. Properties of the gold-sulphur interface: from self-assembled monolayers to clusters.

    Science.gov (United States)

    Bürgi, Thomas

    2015-10-14

    The gold-sulphur interface of self-assembled monolayers (SAMs) was extensively studied some time ago. More recently tremendous progress has been made in the preparation and characterization of thiolate-protected gold clusters. In this feature article we address different properties of the two systems such as their structure, the mobility of the thiolates on the surface and other dynamical aspects, the chirality of the structures and characteristics related to it and their vibrational properties. SAMs and clusters are in the focus of different communities that typically use different experimental approaches to study the respective systems. However, it seems that the nature of the Au-S interfaces in the two cases is quite similar. Recent single crystal X-ray structures of thiolate-protected gold clusters reveal staple motifs characterized by gold ad-atoms sandwiched between two sulphur atoms. This finding contradicts older work on SAMs. However, newer studies on SAMs also reveal ad-atoms. Whether this finding can be generalized remains to be shown. In any case, more and more studies highlight the dynamic nature of the Au-S interface, both on flat surfaces and in clusters. At temperatures slightly above ambient thiolates migrate on the gold surface and on clusters. Evidence for desorption of thiolates at room temperature, at least under certain conditions, has been demonstrated for both systems. The adsorbed thiolate can lead to chirality at different lengths scales, which has been shown both on surfaces and for clusters. Chirality emerges from the organization of the thiolates as well as locally at the molecular level. Chirality can also be transferred from a chiral surface to an adsorbate, as evidenced by vibrational spectroscopy.

  20. Properties of the gold-sulphur interface: from self-assembled monolayers to clusters

    Science.gov (United States)

    Bürgi, Thomas

    2015-09-01

    The gold-sulphur interface of self-assembled monolayers (SAMs) was extensively studied some time ago. More recently tremendous progress has been made in the preparation and characterization of thiolate-protected gold clusters. In this feature article we address different properties of the two systems such as their structure, the mobility of the thiolates on the surface and other dynamical aspects, the chirality of the structures and characteristics related to it and their vibrational properties. SAMs and clusters are in the focus of different communities that typically use different experimental approaches to study the respective systems. However, it seems that the nature of the Au-S interfaces in the two cases is quite similar. Recent single crystal X-ray structures of thiolate-protected gold clusters reveal staple motifs characterized by gold ad-atoms sandwiched between two sulphur atoms. This finding contradicts older work on SAMs. However, newer studies on SAMs also reveal ad-atoms. Whether this finding can be generalized remains to be shown. In any case, more and more studies highlight the dynamic nature of the Au-S interface, both on flat surfaces and in clusters. At temperatures slightly above ambient thiolates migrate on the gold surface and on clusters. Evidence for desorption of thiolates at room temperature, at least under certain conditions, has been demonstrated for both systems. The adsorbed thiolate can lead to chirality at different lengths scales, which has been shown both on surfaces and for clusters. Chirality emerges from the organization of the thiolates as well as locally at the molecular level. Chirality can also be transferred from a chiral surface to an adsorbate, as evidenced by vibrational spectroscopy.

  1. Structures, stabilities, and electronic properties for rare-earth lanthanum doped gold clusters

    International Nuclear Information System (INIS)

    Zhao, Ya-Ru

    2015-01-01

    The structures, stabilities, and electronic properties of rare-earth lanthanum doped gold La 2 Au n (n = 1-9) and pure gold Au n (n ≤ 11) clusters have been investigated by using density functional theory. The optimized geometries show that the lowest energy structures of La 2 Au n clusters favour the 3D structure at n ≥ 3. The lanthanum atoms can strongly enhance the stabilities of gold clusters and tend to occupy the most highly coordinated position. By analysing the gap, vertical ionization potential, and chemical hardness, it is found that the La 2 Au 6 isomer possesses higher stability for small-sized La 2 Au n clusters (n = 1-9). The charges in the La 2 Au n clusters transfer from La atoms to the Au n host. In addition, Wiberg bond indices analysis reveals that the intensity of different bonds of La 2 Au n clusters exhibits a sequence of La-La bond > La-Au bond > Au-Au bond.

  2. Hydrogen-Induced Adsorption of Carbon Monoxide on the Gold Dimer Cation: A Joint Experimental and DFT Investigation.

    Science.gov (United States)

    Vojkovic, Marin; Rayane, Driss; Antoine, Rodolphe; Broyer, Michel; Allouche, Abdul-Rahman; Mignon, Pierre; Dugourd, Philippe

    2017-06-15

    It is demonstrated, using tandem mass spectrometry and radio frequency ion trap, that the adsorption of a H atom on the gold dimer cation, Au 2 H + , prevents its dissociation and allows for adsorption of CO. Reaction kinetics are measured by employing a radio frequency ion trap, where Au 2 + and CO interact for a given reaction time. The effect of a hydrogen atom is evaluated by comparing reaction rate constants measured for Au 2 + and Au 2 H + . The theoretical results for the adsorption of CO molecules and their reaction characteristics with Au 2 + and Au 2 H + are found to agree with the experimental findings. The joint investigations provide insights into hydrogen atom adsorption effects and consequent reaction mechanisms.

  3. From atoms to layers: in situ gold cluster growth kinetics during sputter deposition

    Science.gov (United States)

    Schwartzkopf, Matthias; Buffet, Adeline; Körstgens, Volker; Metwalli, Ezzeldin; Schlage, Kai; Benecke, Gunthard; Perlich, Jan; Rawolle, Monika; Rothkirch, André; Heidmann, Berit; Herzog, Gerd; Müller-Buschbaum, Peter; Röhlsberger, Ralf; Gehrke, Rainer; Stribeck, Norbert; Roth, Stephan V.

    2013-05-01

    The adjustment of size-dependent catalytic, electrical and optical properties of gold cluster assemblies is a very significant issue in modern applied nanotechnology. We present a real-time investigation of the growth kinetics of gold nanostructures from small nuclei to a complete gold layer during magnetron sputter deposition with high time resolution by means of in situ microbeam grazing incidence small-angle X-ray scattering (μGISAXS). We specify the four-stage growth including their thresholds with sub-monolayer resolution and identify phase transitions monitored in Yoneda intensity as a material-specific characteristic. An innovative and flexible geometrical model enables the extraction of morphological real space parameters, such as cluster size and shape, correlation distance, layer porosity and surface coverage, directly from reciprocal space scattering data. This approach enables a large variety of future investigations of the influence of different process parameters on the thin metal film morphology. Furthermore, our study allows for deducing the wetting behavior of gold cluster films on solid substrates and provides a better understanding of the growth kinetics in general, which is essential for optimization of manufacturing parameters, saving energy and resources.The adjustment of size-dependent catalytic, electrical and optical properties of gold cluster assemblies is a very significant issue in modern applied nanotechnology. We present a real-time investigation of the growth kinetics of gold nanostructures from small nuclei to a complete gold layer during magnetron sputter deposition with high time resolution by means of in situ microbeam grazing incidence small-angle X-ray scattering (μGISAXS). We specify the four-stage growth including their thresholds with sub-monolayer resolution and identify phase transitions monitored in Yoneda intensity as a material-specific characteristic. An innovative and flexible geometrical model enables the extraction

  4. Moessbauer studies of non-linear excitations and gold cluster compounds

    International Nuclear Information System (INIS)

    Smit, H.H.A.

    1988-01-01

    Moessbauer effect spectroscopy has been applied to the study of three polynuclear gold cluster compounds. The resulting information on the local vibrational density of states has been compared to several models which take the finite size of the particles into consideration. 188 refs.; 34 figs.; 103 schemes; 8 tabs

  5. Ligand-free gold atom clusters adsorbed on graphene nano sheets generated by oxidative laser fragmentation in water

    Science.gov (United States)

    Lau, Marcus; Haxhiaj, Ina; Wagener, Philipp; Intartaglia, Romuald; Brandi, Fernando; Nakamura, Junji; Barcikowski, Stephan

    2014-08-01

    Over three decades after the first synthesis of stabilized Au55-clusters many scientific questions about gold cluster properties are still unsolved and ligand-free colloidal clusters are difficult to fabricate. Here we present a novel route to produce ultra-small gold particles by using a green technique, the laser ablation and fragmentation in water, without using reductive or stabilizing agents at any step of the synthesis. For fabrication only a pulsed laser, a gold-target, pure water, sodium hydroxide and hydrogen peroxide are deployed. The particles are exemplarily hybridized to graphene supports showing that these carbon-free colloidal clusters might serve as versatile building blocks.

  6. Gold clusters sliding on graphite: a possible quartz crystal microbalance experiment?

    International Nuclear Information System (INIS)

    Pisov, S; Tosatti, E; Tartaglino, U; Vanossi, A

    2007-01-01

    A large measured two-dimensional (2D) diffusion coefficient of gold nanoclusters on graphite has been known experimentally and theoretically for about a decade. When subjected to a lateral force, these clusters should slide with an amount of friction that can be measured. We examine the hypothetical possibility of measuring by quartz crystal microbalance (QCM) the phononic sliding friction of gold clusters in the size range around 250 atoms on a graphite substrate between 300 and 600 K. Assuming the validity of Einstein's relations of ordinary Brownian motion and making use of the experimentally available activated behaviour of the diffusion coefficients, we can predict the sliding friction and slip times as a function of temperature. It is found that a prototypical deposited gold cluster could yield slip times at the standard measurable size of 10 -9 s for temperatures around 450-500 K, or 200 0 C. Since gold nanoclusters may also melt at around these temperatures, QCM could offer the additional chance of observing this phenomenon through a frictional change

  7. Permanent magnetism in phosphine- and chlorine-capped gold: from clusters to nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Munoz-Marquez, Miguel A., E-mail: miguel.angel@icmse.csic.es; Guerrero, Estefania; Fernandez, Asuncion [Instituto de Ciencia de Materiales de Sevilla (CSIC-US) (Spain); Crespo, Patricia; Hernando, Antonio [Instituto de Magnetismo Aplicado (UCM-ADIF-CSIC) (Spain); Lucena, Raquel; Conesa, Jose C. [Instituto de Catalisis y Petroleoquimica (CSIC) (Spain)

    2010-05-15

    Magnetometry results have shown that gold NPs ({approx}2 nm in size) protected with phosphine and chlorine ligands exhibit permanent magnetism. When the NPs size decreases down to the subnanometric size range, e.g. undecagold atom clusters, the permanent magnetism disappears. The near edge structure of the X-ray absorption spectroscopy data points out that charge transfer between gold and the capping system occurs in both cases. These results strongly suggest that nearly metallic Au bonds are also required for the induction of a magnetic response. Electron paramagnetic resonance observations indicate that the contribution to magnetism from eventual iron impurities can be disregarded.

  8. Non-linear sputtering effects induced by MeV energy gold clusters

    International Nuclear Information System (INIS)

    Boussofiane-Baudin, K.; Brunelle, A.; Chaurand, P.; Della-Negra, S.; Depauw, J.; Le Beyec, Y.; Hakansson, P.

    1993-09-01

    Gold clusters Au n + with 1 < n ≤ 4, accelerated to MeV energies at the Orsay tandem accelerator, have been used to induce secondary ion emission from the surface of thin organic and inorganic films. A non-linear enhancement of the secondary ion yields is observed when cluster impacts are compared to single atom impacts at the same velocity. It has been shown that the collective effects propagate in the solid over a depth larger than 2000 A. The equilibrium charge state of cluster constituents after their passage through a thin carbon foil (1000 A) has been measured. The mean value for the cluster constituents is the same as for single atoms at the same velocity. (authors). 41 refs., 8 figs., 1 tab

  9. Influence of gold nanoparticles of varying size in improving the lipase activity within cationic reverse micelles.

    Science.gov (United States)

    Maiti, Subhabrata; Das, Dibyendu; Shome, Anshupriya; Das, Prasanta Kumar

    2010-02-08

    Herein, we report the effect of gold nanoparticles (GNPs) in enhancing lipase activity in reverse micelles of cetyltrimethylammonium bromide (CTAB)/water/isooctane/n-hexanol. The size and concentration of the nanoparticles were varied and their specific roles were assessed in detail. An overall enhancement of activity was observed in the GNP-doped CTAB reverse micelles. The improvement in activity becomes more prominent with increasing concentration and size of the GNPs (0-52 microM and ca. 3-30 nm, respectively). The observed highest lipase activity (k(2)=1070+/-12 cm(3) g(-1) s(-1)) in GNP-doped CTAB reverse micelles ([GNP]: 52 microm, ca. 20 nm) is 2.5-fold higher than in CTAB reverse micelles without GNPs. Improvement in the lipase activity is only specific to the GNP-doped reverse micellar media, whereas GNP deactivates and structurally deforms the enzyme in aqueous media. The reason for this activation is probably due to the formation of larger-sized reverse micelles in which the GNP acts as a polar core and the surfactants aggregate around the nanoparticle ('GNP pool') instead of only water. Lipase at the augmented interface of the GNP-doped reverse micelle showed improved activity because of enhancement in both the substrate and enzyme concentrations and increased flexibility in the lipase conformation. The extent of the activation is greater in the case of the larger-sized GNPs. A correlation has been established between the activity of lipase and its secondary structure by using circular dichroism and FTIR spectroscopic analysis. The generalized influence of GNP is verified in the reverse micelles of another surfactant, namely, cetyltripropylammonium bromide (CTPAB). TEM, dynamic light scattering (DLS), and UV/Vis spectroscopic analysis were utilized to characterize the GNPs and the organized aggregates. For the first time, CTAB-based reverse micelles have been found to be an excellent host for lipase simply by doping with appropriately sized GNPs.

  10. Molecular geometries and relative stabilities of titanium oxide and gold-titanium oxide clusters

    Energy Technology Data Exchange (ETDEWEB)

    Hudson, Rohan J.; Falcinella, Alexander; Metha, Gregory F., E-mail: greg.metha@adelaide.edu.au

    2016-09-30

    Titanium oxide and gold-titanium oxide clusters of stoichiometry M{sub x}O{sub y} (M{sub x} = Ti{sub 3}, Ti{sub 4} & AuTi{sub 3}; y = 0 − (2x + 2)) have been investigated using density functional theory. Geometries of determined global energy minimum structures are reported and other isomers predicted up to 0.5 eV higher in energy. The Ti{sub 3}O{sub n} geometries build upon a triangular Ti{sub 3} motif, while Ti{sub 4}O{sub n} stoichiometries template upon a pseudo-tetrahedral Ti{sub 4} structure. Addition of a gold atom to the Ti{sub 3}O{sub n} series does not significantly alter the cluster geometry, with the gold atom preferentially binding to titanium atoms over oxygen atoms. Adiabatic ionization energies, electron affinities and HOMO/LUMO energies increase in magnitude with increasing oxygenation. The HOMO-LUMO energy gaps reach the bulk anatase band gap energy at stoichiometry (Au)Ti{sub m}O{sub 2m−1}, and increase above this upon further oxygen addition. The most stable structural moieties are found to be a cage-like, C{sub 3v} symmetric Ti{sub 4}O{sub 6/7} geometry and a Ti{sub 3}O{sub 6} structure with an η{sup 3}-bound oxygen atom.

  11. Fluorescence Imaging Assisted Photodynamic Therapy Using Photosensitizer-Linked Gold Quantum Clusters.

    Science.gov (United States)

    Nair, Lakshmi V; Nazeer, Shaiju S; Jayasree, Ramapurath S; Ajayaghosh, Ayyappanpillai

    2015-06-23

    Fluorescence imaging assisted photodynamic therapy (PDT) is a viable two-in-one clinical tool for cancer treatment and follow-up. While the surface plasmon effect of gold nanorods and nanoparticles has been effective for cancer therapy, their emission properties when compared to gold nanoclusters are weak for fluorescence imaging guided PDT. In order to address the above issues, we have synthesized a near-infrared-emitting gold quantum cluster capped with lipoic acid (L-AuC with (Au)18(L)14) based nanoplatform with excellent tumor reduction property by incorporating a tumor-targeting agent (folic acid) and a photosensitizer (protoporphyrin IX), for selective PDT. The synthesized quantum cluster based photosensitizer PFL-AuC showed 80% triplet quantum yield when compared to that of the photosensitizer alone (63%). PFL-AuC having 60 μg (0.136 mM) of protoporphyrin IX was sufficient to kill 50% of the tumor cell population. Effective destruction of tumor cells was evident from the histopathology and fluorescence imaging, which confirm the in vivo PDT efficacy of PFL-AuC.

  12. The weak lensing analysis of the CFHTLS and NGVS RedGOLD galaxy clusters

    Science.gov (United States)

    Parroni, C.; Mei, S.; Erben, T.; Van Waerbeke, L.; Raichoor, A.; Ford, J.; Licitra, R.; Meneghetti, M.; Hildebrandt, H.; Miller, L.; Côté, P.; Covone, G.; Cuillandre, J.-C.; Duc, P.-A.; Ferrarese, L.; Gwyn, S. D. J.; Puzia, T. H.

    2017-12-01

    An accurate estimation of galaxy cluster masses is essential for their use in cosmological and astrophysical studies. We studied the accuracy of the optical richness obtained by our RedGOLD cluster detection algorithm tep{licitra2016a, licitra2016b} as a mass proxy, using weak lensing and X-ray mass measurements. We measured stacked weak lensing cluster masses for a sample of 1323 galaxy clusters in the Canada-France-Hawaii Telescope Legacy Survey W1 and the Next Generation Virgo Cluster Survey at 0.2z<0.5, in the optical richness range 10-70. We tested different weak lensing mass models that account for miscentering, non-weak shear, the two-halo term, the contribution of the Brightest Cluster Galaxy, and the intrinsic scatter in the mass-richness relation. We calculated the coefficients of the mass-richness relation, and of the scaling relations between the lensing mass and X-ray mass proxies.

  13. ClbM is a versatile, cation-promiscuous MATE transporter found in the colibactin biosynthetic gene cluster

    International Nuclear Information System (INIS)

    Mousa, Jarrod J.; Newsome, Rachel C.; Yang, Ye; Jobin, Christian; Bruner, Steven D.

    2017-01-01

    Multidrug transporters play key roles in cellular drug resistance to toxic molecules, yet these transporters are also involved in natural product transport as part of biosynthetic clusters in bacteria and fungi. The genotoxic molecule colibactin is produced by strains of virulent and pathobiont Escherichia coli and Klebsiella pneumoniae. In the biosynthetic cluster is a multidrug and toxic compound extrusion protein (MATE) proposed to transport the prodrug molecule precolibactin across the cytoplasmic membrane, for subsequent cleavage by the peptidase ClbP and cellular export. We recently determined the X-ray structure of ClbM, and showed preliminary data suggesting its specific role in precolibactin transport. Here, we define a functional role of ClbM by examining transport capabilities under various biochemical conditions. Our data indicate ClbM responds to sodium, potassium, and rubidium ion gradients, while also having substantial transport activity in the absence of alkali cations. - Highlights: • ClbM is a cation promiscuous MATE multidrug transporter. • The role of key residues were identified in both the cation and proton binding. • The biologically relevant substrate for ClbM is the natural product precolibactin.

  14. Influence of the photothermal effect of a gold nanorod cluster on biofilm disinfection

    International Nuclear Information System (INIS)

    Jo, Wonjin; Kim, Min Jun

    2013-01-01

    We evaluate a method for biofilm disinfection by raising biofilm temperature using the photothermal effect of a gold nanorod cluster. Gold nanorods (GNRs) are capable of generating enough heat to lyse bacteria by heating biofilm via laser irradiation. To test this, GNRs are synthesized using wet chemistry and a single GNR cluster is fabricated using photo-lithography technique. The GNR cluster is directly applied to the biofilm and its effects on bacteria are measured before and after laser irradiation. The photothermal effect of GNRs on the biofilm structure results in a considerable reduction of cell viability and biofilm thickness. Several quantitative measurements of bacterial mortality and biofilm destruction show an increase in efficacy with increasing durations of laser irradiation. Scanning electron microscopy images of the irradiated bacteria show obvious morphological damage such as rupture or collapse of the bacterial cell membrane in the biofilm. These results indicate that GNRs are useful and a potential material for use in photothermal treatments, particularly biofilm disinfection. (paper)

  15. Determination of the structures of small gold clusters on stepped magnesia by density functional calculations.

    Science.gov (United States)

    Damianos, Konstantina; Ferrando, Riccardo

    2012-02-21

    The structural modifications of small supported gold clusters caused by realistic surface defects (steps) in the MgO(001) support are investigated by computational methods. The most stable gold cluster structures on a stepped MgO(001) surface are searched for in the size range up to 24 Au atoms, and locally optimized by density-functional calculations. Several structural motifs are found within energy differences of 1 eV: inclined leaflets, arched leaflets, pyramidal hollow cages and compact structures. We show that the interaction with the step clearly modifies the structures with respect to adsorption on the flat defect-free surface. We find that leaflet structures clearly dominate for smaller sizes. These leaflets are either inclined and quasi-horizontal, or arched, at variance with the case of the flat surface in which vertical leaflets prevail. With increasing cluster size pyramidal hollow cages begin to compete against leaflet structures. Cage structures become more and more favourable as size increases. The only exception is size 20, at which the tetrahedron is found as the most stable isomer. This tetrahedron is however quite distorted. The comparison of two different exchange-correlation functionals (Perdew-Burke-Ernzerhof and local density approximation) show the same qualitative trends. This journal is © The Royal Society of Chemistry 2012

  16. Efficient visible light photocatalytic NO{sub x} removal with cationic Ag clusters-grafted (BiO){sub 2}CO{sub 3} hierarchical superstructures

    Energy Technology Data Exchange (ETDEWEB)

    Feng, Xin [Chongqing Key Laboratory of Catalysis and Functional Organic Molecules, College of Environment and Resources, Engineering Research Center for Waste Oil Recovery Technology and Equipment of Ministry of Education, College of Environment and Resources, Chongqing Technology and Business University, Chongqing 40067 (China); Zhang, Wendong [Department of Scientific Research Management, Chongqing Normal University, Chongqing 401331 (China); Deng, Hua [State Key Joint Laboratory of Environment Simulation and Pollution Control, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085 (China); Ni, Zilin [Department of Scientific Research Management, Chongqing Normal University, Chongqing 401331 (China); Dong, Fan, E-mail: dfctbu@126.com [Chongqing Key Laboratory of Catalysis and Functional Organic Molecules, College of Environment and Resources, Engineering Research Center for Waste Oil Recovery Technology and Equipment of Ministry of Education, College of Environment and Resources, Chongqing Technology and Business University, Chongqing 40067 (China); Zhang, Yuxin, E-mail: zhangyuxin@cqu.edu.cn [College of Materials Science and Engineering, National Key Laboratory of Fundamental Science of Micro/Nano-Devices and System Technology, Chongqing University, Chongqing 400044 (China)

    2017-01-15

    Graphical abstract: The cationic Ag clusters-grafted (BiO){sub 2}CO{sub 3} hierarchical superstructures exhibits highly enhanced visible light photocatalytic air purification through an interfacial charge transfer process induced by Ag clusters. - Highlights: • Microstructural optimization and surface cluster-grafting were firstly combined. • Cationic Ag clusters were grafted on the surface of (BiO){sub 2}CO{sub 3} superstructures. • The Ag clusters-grafted BHS displayed enhanced visible light photocatalysis. • Direct interfacial charge transfer (IFCT) from BHS to Ag clusters was proposed. • The charge transfer process and the dominant reactive species were revealed. - Abstract: A facile method was developed to graft cationic Ag clusters on (BiO){sub 2}CO{sub 3} hierarchical superstructures (BHS) surface to improve their visible light activity. Significantly, the resultant Ag clusters-grafted BHS displayed a highly enhanced visible light photocatalytic performance for NOx removal due to the direct interfacial charge transfer (IFCT) from BHS to Ag clusters. The chemical and coordination state of the cationic Ag clusters was determined with the extended X-ray absorption fine structure (EXAFS) and a theoretical structure model was proposed for this unique Ag clusters. The charge transfer process and the dominant reactive species (·OH) were revealed on the basis of electron spin resonance (ESR) trapping. A new photocatalysis mechanism of Ag clusters-grafted BHS under visible light involving IFCT process was uncovered. In addition, the cationic Ag clusters-grafted BHS also demonstrated high photochemical and structural stability under repeated photocatalysis runs. The perspective of enhancing photocatalysis through combination of microstructural optimization and IFCT could provide a new avenue for the developing efficient visible light photocatalysts.

  17. Ab initio dynamics and photoionization mass spectrometry reveal ion-molecule pathways from ionized acetylene clusters to benzene cation.

    Science.gov (United States)

    Stein, Tamar; Bandyopadhyay, Biswajit; Troy, Tyler P; Fang, Yigang; Kostko, Oleg; Ahmed, Musahid; Head-Gordon, Martin

    2017-05-23

    The growth mechanism of hydrocarbons in ionizing environments, such as the interstellar medium (ISM), and some combustion conditions remains incompletely understood. Ab initio molecular dynamics (AIMD) simulations and molecular beam vacuum-UV (VUV) photoionization mass spectrometry experiments were performed to understand the ion-molecule growth mechanism of small acetylene clusters (up to hexamers). A dramatic dependence of product distribution on the ionization conditions is demonstrated experimentally and understood from simulations. The products change from reactive fragmentation products in a higher temperature, higher density gas regime toward a very cold collision-free cluster regime that is dominated by products whose empirical formula is (C 2 H 2 ) n + , just like ionized acetylene clusters. The fragmentation products result from reactive ion-molecule collisions in a comparatively higher pressure and temperature regime followed by unimolecular decomposition. The isolated ionized clusters display rich dynamics that contain bonded C 4 H 4 + and C 6 H 6 + structures solvated with one or more neutral acetylene molecules. Such species contain large amounts (>2 eV) of excess internal energy. The role of the solvent acetylene molecules is to affect the barrier crossing dynamics in the potential energy surface (PES) between (C 2 H 2 ) n + isomers and provide evaporative cooling to dissipate the excess internal energy and stabilize products including the aromatic ring of the benzene cation. Formation of the benzene cation is demonstrated in AIMD simulations of acetylene clusters with n > 3, as well as other metastable C 6 H 6 + isomers. These results suggest a path for aromatic ring formation in cold acetylene-rich environments such as parts of the ISM.

  18. Ab initio dynamics and photoionization mass spectrometry reveal ion–molecule pathways from ionized acetylene clusters to benzene cation

    Science.gov (United States)

    Stein, Tamar; Bandyopadhyay, Biswajit; Troy, Tyler P.; Fang, Yigang; Kostko, Oleg

    2017-01-01

    The growth mechanism of hydrocarbons in ionizing environments, such as the interstellar medium (ISM), and some combustion conditions remains incompletely understood. Ab initio molecular dynamics (AIMD) simulations and molecular beam vacuum-UV (VUV) photoionization mass spectrometry experiments were performed to understand the ion–molecule growth mechanism of small acetylene clusters (up to hexamers). A dramatic dependence of product distribution on the ionization conditions is demonstrated experimentally and understood from simulations. The products change from reactive fragmentation products in a higher temperature, higher density gas regime toward a very cold collision-free cluster regime that is dominated by products whose empirical formula is (C2H2)n+, just like ionized acetylene clusters. The fragmentation products result from reactive ion–molecule collisions in a comparatively higher pressure and temperature regime followed by unimolecular decomposition. The isolated ionized clusters display rich dynamics that contain bonded C4H4+ and C6H6+ structures solvated with one or more neutral acetylene molecules. Such species contain large amounts (>2 eV) of excess internal energy. The role of the solvent acetylene molecules is to affect the barrier crossing dynamics in the potential energy surface (PES) between (C2H2)n+ isomers and provide evaporative cooling to dissipate the excess internal energy and stabilize products including the aromatic ring of the benzene cation. Formation of the benzene cation is demonstrated in AIMD simulations of acetylene clusters with n > 3, as well as other metastable C6H6+ isomers. These results suggest a path for aromatic ring formation in cold acetylene-rich environments such as parts of the ISM. PMID:28484019

  19. Gold atomic cluster mediated electrochemical aptasensor for the detection of lipopolysaccharide.

    Science.gov (United States)

    Posha, Biyas; Nambiar, Sindhu R; Sandhyarani, N

    2018-03-15

    We have constructed an aptamer immobilized gold atomic cluster mediated, ultrasensitive electrochemical biosensor (Apt/AuAC/Au) for LPS detection without any additional signal amplification strategy. The aptamer self-assemble onto the gold atomic clusters makes Apt/AuAC/Au an excellent platform for the LPS detection. Differential pulse voltammetry and EIS were used for the quantitative LPS detection. The Apt/AuAC/Au sensor offers an ultrasensitive and selective detection of LPS down to 7.94 × 10 -21 M level with a wide dynamic range from 0.01 attomolar to 1pM. The sensor exhibited excellent selectivity and stability. The real sample analysis was performed by spiking the diluted insulin sample with various concentration of LPS and obtained recovery within 2% error value. The sensor is found to be more sensitive than most of the literature reports. The simple and easy way of construction of this sensor provides an efficient and promising detection of an even trace amount of LPS. Copyright © 2017 Elsevier B.V. All rights reserved.

  20. Design, Synthesis, and Characterization of Novel Thiol-Derivatized Ibuprofen Monolayer Protected Gold Clusters

    International Nuclear Information System (INIS)

    Lee, K.H.; Lee, K.H.; Lin, Y.Sh.; Huang, P.J.

    2013-01-01

    A series of new thiol-derivatized ibuprofen monolayer protected gold clusters have been prepared by amidation of ibuprofen with alkyl alcohol or aminophenol affording the carboxamide, N-hydroxyalkyl amide 2, and N-hydroxyphenyl amide 6, which were then tosylate with p-toluenesulfonyl chloride at hydroxyl group to give 3 and 7. Reactions of 3 and 7 with NaSH afforded the mercapto derivatives 4 and 8. Conducting Brust’s reaction with a 3:1 mole ratio of thiolate ibuprofen/ AuCl 4 - yielded polydisperse thiol-derivatized ibuprofen-MPCs 5 and 9. All compounds have been identified by NMR, MS, UV, and IR spectroscopies. Compounds 4 and 8 and the MPCs 5 and 9 have been investigated by using the method of 1 H NMR spectroscopy. The broadening of the signals from 0.8 to 2.0 ppm in 1 H NMR spectrum of MPCs 5 and 9 confirmed the success of the conjugation of thiol-containing derivatives with nano gold cluster.

  1. ClbM is a versatile, cation-promiscuous MATE transporter found in the colibactin biosynthetic gene cluster.

    Science.gov (United States)

    Mousa, Jarrod J; Newsome, Rachel C; Yang, Ye; Jobin, Christian; Bruner, Steven D

    2017-01-22

    Multidrug transporters play key roles in cellular drug resistance to toxic molecules, yet these transporters are also involved in natural product transport as part of biosynthetic clusters in bacteria and fungi. The genotoxic molecule colibactin is produced by strains of virulent and pathobiont Escherichia coli and Klebsiella pneumoniae. In the biosynthetic cluster is a multidrug and toxic compound extrusion protein (MATE) proposed to transport the prodrug molecule precolibactin across the cytoplasmic membrane, for subsequent cleavage by the peptidase ClbP and cellular export. We recently determined the X-ray structure of ClbM, and showed preliminary data suggesting its specific role in precolibactin transport. Here, we define a functional role of ClbM by examining transport capabilities under various biochemical conditions. Our data indicate ClbM responds to sodium, potassium, and rubidium ion gradients, while also having substantial transport activity in the absence of alkali cations. Copyright © 2016 Elsevier Inc. All rights reserved.

  2. Detection of gold cluster ions by ion-to-ion conversion using a CsI-converter

    International Nuclear Information System (INIS)

    Nguyen, V.-T.; Novilkov, A.C.; Obnorskii, V.V.

    1997-01-01

    Gold cluster ions in the m/z range of 10 4 -2 x 10 6 u were produced by bombarding a thin film of gold with 252 Cf-fission fragments. The gold covering a C-Al substrate formed islets having a mean diameter of 44 A. Their size- and mass-distribution was determined by means of electron microscopy. The main task was to measure the m/z distribution of the cluster ions ejected from the sample surface. For this purpose we built a time-of-flight (TOF) mass spectrometer, which could be used as a linear TOF instrument or, alternatively, as a tandem-TOF instrument being equipped with an ion-to-ion converter. Combining the results obtained in both modes, it turned out that the linear TOF instrument equipped with micro-channel plates had a mean detection efficiency for 20 keV cluster ions of about 40%. In the tandem mode, the cluster ions hit a CsI converter with energies of 40z keV (z = charge state), from where secondary ions - mainly Cs + and (CsI) n Cs + cluster ions - were ejected. These ions were used to measure the TOF spectrum of the gold cluster ions. The detection efficiency of the cluster ions was found to vary in the available mass range from 99.7% to 96.5%. The complete mass distribution between 4 x 10 4 and 4 x 10 6 u was determined and compared with the corresponding mass distribution of the gold islets covering the substrate. (orig.)

  3. Chemistry and kinetics of size-selected cobalt cluster cations at thermal energies. I. Reactions with CO

    Science.gov (United States)

    Guo, B. C.; Kerns, K. P.; Castleman, A. W., Jr.

    1992-06-01

    The chemistry and kinetics of size-selected Co+n cluster-ion (n=2-8) reactions with CO are studied using a selected ion drift tube affixed with a laser vaporization source operated under well-defined thermal conditions. All reactions studied in the present work are found to be association reactions. Their absolute rate constants, which are determined quantitatively, are found to have a strong dependence on cluster size. Similar to the cases of reactions with many other reactants such as H2 and CH4, Co+4 and Co+5 display a higher reactivity toward the CO molecule than do clusters of neighboring size. The multiple-collision conditions employed in the present work have enabled a determination of the maximum coordination number of CO molecules bound onto each Co+n cluster. It is found that the tetramer tends to bond 12 CO molecules, the pentamer 14 CO, hexamer 16 CO, and so on. The results are interpreted in terms of Lauher's calculation and the polyhedral skeletal electron pair theory. All the measured maximum coordination numbers correlate extremely well with the predictions of these theories, except for the trimer where the measured number is one CO less than the predicted value. The good agreement between experiment and theory enables one to gain some insight into the geometric structure of the clusters. Based on the present findings, the cobalt tetramer cation is interpreted to have a tetrahedral structure, the pentamer a trigonal bipyramid, and the hexamer an octahedral structure. Other cluster structures are also discussed.

  4. Dual effects of water vapor on ceria-supported gold clusters.

    Science.gov (United States)

    Li, Zhimin; Li, Weili; Abroshan, Hadi; Ge, Qingjie; Li, Gao; Jin, Rongchao

    2018-04-05

    Atomically precise nanocatalysts are currently being intensely pursued in catalysis research. Such nanocatalysts can serve as model catalysts for gaining fundamental insights into catalytic processes. In this work we report a discovery that water vapor provokes the mild removal of surface long-chain ligands on 25-atom Au25(SC12H25)18 nanoclusters in a controlled manner. Using the resultant Au25(SC12H25)18-x/CeO2 catalyst and CO oxidation as a probe reaction, we found that the catalytic activity of cluster/CeO2 is enhanced from nearly zero conversion of CO (in the absence of water) to 96.2% (in the presence of 2.3 vol% H2O) at the same temperature (100 °C). The cluster catalysts exhibit high stability during the CO oxidation process under moisture conditions (up to 20 vol% water vapor). Water vapor plays a dual role in gold cluster-catalyzed CO oxidation. FT-IR and XPS analyses in combination with density functional theory (DFT) simulations suggest that the "-SC12H25" ligands are easier to be removed under a water vapor atmosphere, thus generating highly active sites. Moreover, the O22- peroxide species constitutes the active oxygen species in CO oxidation, evidenced by Raman spectroscopy analysis and isotope experiments on the CeO2 and cluster/CeO2. The results also indicate the perimeter sites of the interface of Au25(SC12H25)18-x/CeO2 to be active sites for catalytic CO oxidation. The controlled exposure of active sites under mild conditions is of critical importance for the utilization of clusters in catalysis.

  5. Controlled AFM detachments and movement of nanoparticles: gold clusters on HOPG at different temperatures.

    Science.gov (United States)

    Tripathi, Manoj; Paolicelli, Guido; D'Addato, Sergio; Valeri, Sergio

    2012-06-22

    The effect of temperature on the onset of movement of gold nanoclusters (diameter 27 nm) deposited on highly oriented pyrolytic graphite (HOPG) has been studied by atomic force microscopy (AFM) techniques. Using the AFM with amplitude modulation (tapping mode AFM) we have stimulated and controlled the movement of individual clusters. We show how, at room temperature, controlled detachments and smooth movements can be obtained for clusters having dimensions comparable to or smaller than the tip radius. Displacement is practically visible in real time and it can be started and stopped easily by adjusting only one parameter, the tip amplitude oscillation. Analysing the energy dissipation signal at the onset of nanocluster sliding we evaluated a detachment threshold energy as a function of temperature in the range 300-413 K. We also analysed single cluster thermal induced displacement and combining this delicate procedure with AFM forced movement behaviour we conclude that detachment threshold energy is directly related to the activation energy of nanocluster diffusion and it scales linearly with temperature as expected for a single-particle thermally activated process.

  6. Thermal Methane Conversion to Syngas Mediated by Rh1-Doped Aluminum Oxide Cluster Cations RhAl3O4.

    Science.gov (United States)

    Li, Ya-Ke; Yuan, Zhen; Zhao, Yan-Xia; Zhao, Chongyang; Liu, Qing-Yu; Chen, Hui; He, Sheng-Gui

    2016-10-05

    Laser ablation generated RhAl 3 O 4 + heteronuclear metal oxide cluster cations have been mass-selected using a quadrupole mass filter and reacted with CH 4 or CD 4 in a linear ion trap reactor under thermal collision conditions. The reactions have been characterized by state-of-the-art mass spectrometry and quantum chemistry calculations. The RhAl 3 O 4 + cluster can activate four C-H bonds of a methane molecule and convert methane to syngas, an important intermediate product in methane conversion to value-added chemicals. The Rh atom is the active site for activation of the C-H bonds of methane. The high electron-withdrawing capability of Rh atom is the driving force to promote the conversion of methane to syngas. The polarity of Rh oxidation state is changed from positive to negative after the reaction. This study has provided the first example of methane conversion to syngas by heteronuclear metal oxide clusters under thermal collision conditions. Furthermore, the molecular level origin has been revealed for the condensed-phase experimental observation that trace amounts of Rh can promote the participation of lattice oxygen of chemically very inert support (Al 2 O 3 ) to oxidize methane to carbon monoxide.

  7. Synthesis and Molecular Structure of a Novel Compound Containing a Carbonate-Bridged Hexacalcium Cluster Cation Assembled on a Trimeric Trititanium(IV)-Substituted Wells-Dawson Polyoxometalate.

    Science.gov (United States)

    Hoshino, Takahiro; Isobe, Rina; Kaneko, Takuya; Matsuki, Yusuke; Nomiya, Kenji

    2017-08-21

    A novel compound containing a hexacalcium cluster cation, one carbonate anion, and one calcium cation assembled on a trimeric trititanium(IV)-substituted Wells-Dawson polyoxometalate (POM), [{Ca 6 (CO 3 )(μ 3 -OH)(OH 2 ) 18 }(P 2 W 15 Ti 3 O 61 ) 3 Ca(OH 2 ) 3 ] 19- (Ca 7 Ti 9 Trimer), was obtained as the Na 7 Ca 6 salt (NaCa-Ca 7 Ti 9 Trimer) by the reaction of calcium chloride with the monomeric trititanium(IV)-substituted Wells-Dawson POM species "[P 2 W 15 Ti 3 O 59 (OH) 3 ] 9- " (Ti 3 Monomer). Ti 3 Monomer was generated in situ under basic conditions from the separately prepared tetrameric species with bridging Ti(OH 2 ) 3 groups and an encapsulated Cl - ion, [{P 2 W 15 Ti 3 O 59 (OH) 3 } 4 {μ 3 -Ti(H 2 O) 3 } 4 Cl] 21- (Ti 16 Tetramer). The Na 7 Ca 6 salt of Ca 7 Ti 9 Trimer was characterized by complete elemental analysis, thermogravimetric (TG) and differential thermal analyses (DTA), FTIR, single-crystal X-ray structure analysis, and solution 183 W and 31 P NMR spectroscopy. X-ray crystallography revealed that the [Ca 6 (CO 3 )(μ 3 -OH)(OH 2 ) 18 ] 9+ cluster cation was composed of six calcium cations linked by one μ 6 -carbonato anion and one μ 3 -OH - anion. The cluster cation was assembled, together with one calcium ion, on a trimeric species composed of three tri-Ti(IV)-substituted Wells-Dawson subunits linked by Ti-O-Ti bonds. Ca 7 Ti 9 Trimer is an unprecedented POM species containing an alkaline-earth-metal cluster cation and is the first example of alkaline-earth-metal ions clustered around a titanium(IV)-substituted POM.

  8. Gold Cluster Diffusion Kinetics on Stoichiometric and Reduced Surfaces of Rutile TiO 2 (110)

    Energy Technology Data Exchange (ETDEWEB)

    Goldman, Nir; Browning, Nigel D.

    2011-06-16

    Gold clusters on rutile TiO2 are known to serve as efficient oxidation catalysts for pollutants and environmental contaminants. However, the mechanism by which highly mobile small clusters migrate and aggregate into larger species relevant to gold’s catalytic activity remains unresolved. We report herein on ab initio simulations of the diffusion of atomic gold clusters up to the trimer on rutile TiO2(110) surfaces. We show that, on the stoichiometric surface, both the dimer and the trimer can exhibit relatively low surface mobility due to high energetic barriers for diffusion out of their energetic minima coupled with low barriers for the reverse motion. On the reduced surface, these clusters can diffuse relatively quickly between energetic minima within the oxygen vacancy site due to the large degree of vibrational entropy in their transition states. Our computed diffusion times provide a point of comparison for future experiments and will aid in development of models of gold cluster island sintering.

  9. Far-infrared spectra of yttrium-doped gold clusters Au(n)Y (n=1-9).

    Science.gov (United States)

    Lin, Ling; Claes, Pieterjan; Gruene, Philipp; Meijer, Gerard; Fielicke, André; Nguyen, Minh Tho; Lievens, Peter

    2010-06-21

    The geometric, spectroscopic, and electronic properties of neutral yttrium-doped gold clusters Au(n)Y (n=1-9) are studied by far-infrared multiple photon dissociation (FIR-MPD) spectroscopy and quantum chemical calculations. Comparison of the observed and calculated vibrational spectra allows the structures of the isomers present in the molecular beam to be determined. Most of the isomers for which the IR spectra agree best with experiment are calculated to be the energetically most stable ones. Attachment of xenon to the Au(n)Y cluster can cause changes in the IR spectra, which involve band shifts and band splittings. In some cases symmetry changes, as a result of the attachment of xenon atoms, were also observed. All the Au(n)Y clusters considered prefer a low spin state. In contrast to pure gold clusters, which exhibit exclusively planar lowest-energy structures for small sizes, several of the studied species are three-dimensional. This is particularly the case for Au(4)Y and Au(9)Y, while for some other sizes (n=5, 8) the 3D structures have an energy similar to that of their 2D counterparts. Several of the lowest-energy structures are quasi-2D, that is, slightly distorted from planar shapes. For all the studied species the Y atom prefers high coordination, which is different from other metal dopants in gold clusters.

  10. Cluster formation of network-modifier cations in cesium silicate glasses

    Science.gov (United States)

    Jardón-Álvarez, Daniel; Sanders, Kevin J.; Phyo, Pyae; Baltisberger, Jay H.; Grandinetti, Philip J.

    2018-03-01

    Natural abundance 29Si two-dimensional magic-angle flipping (2D MAF) NMR spectra were measured in a series of ten cesium silicate glass compositions xCs2O.(1 - x)SiO2, where x is 0.067, 0.113, 0.175, 0.179, 0.218, 0.234, 0.263, 0.298, 0.31, and 0.36. The Q3 shielding anisotropy decreases with increasing Cs content—interpreted as an increase in the non-bridging oxygen (NBO) bond length from increasing Cs coordination (clustering) around the NBO. The 29Si 2D MAF spectra for four glass compositions x = 0.218, 0.234, 0.263, 0.298 exhibit a second co-existing and distinctly smaller shielding anisotropy corresponding to a significantly longer Si-NBO length arising from a higher degree of Cs clustering around the NBO. This second Q3 site appears at a Cs2O mole fraction close to the critical mole fraction of x = 0.24 associated with the percolation threshold of non-bridging oxygen in random close packing of oxygen, thus suggesting that the longer Si-NBO length is associated with an infinite size spanning cluster while the sites with larger anisotropies are associated with shorter Si-NBO lengths and belong to finite size clusters. The equilibrium constant of the Q3 disproportionation reaction was determined as k3 = 0.005, indicating a Qn anionic species distribution close to a binary model as expected for a low field strength modifier such as cesium. It is also found that evolution of the isotropic Q4 and line shapes with increasing Cs content are consistent with a random connectivity model between Qn of differing number of bridging oxygen, n.

  11. Lipophilic phosphorescent gold(I) clusters as selective probes for visualization of lipid droplets by two-photon microscopy

    Czech Academy of Sciences Publication Activity Database

    Koshel, E. I.; Cheluskin, P. S.; Melnikov, A. S.; Serdobintsev, P. Y.; Stolbovaia, A. Y.; Saifitdinova, A. F.; Scheslavskiy, V. I.; Chernyavskiy, Oleksandr; Gaginskaya, E. R.; Koshevoy, I. O.; Tunik, S. P.

    2017-01-01

    Roč. 332, Jan 1 (2017), s. 122-130 ISSN 1010-6030 R&D Projects: GA MŠk(CZ) LM2015062 Institutional support: RVO:67985823 Keywords : polynuclear gold-alkynyl cluster * lipophilic probe * phosphorescence * adipocyte * two-photon microscopy * PLIM Subject RIV: EB - Genetics ; Molecular Biology OBOR OECD: Medical laboratory technology (including laboratory samples analysis Impact factor: 2.625, year: 2016

  12. AlPcS4-PDT for gastric cancer therapy using gold nanorod, cationic liposome, and Pluronic® F127 nanomicellar drug carriers.

    Science.gov (United States)

    Xin, Jing; Wang, Sijia; Wang, Bing; Wang, Jiazhuang; Wang, Jing; Zhang, Luwei; Xin, Bo; Shen, Lijian; Zhang, Zhenxi; Yao, Cuiping

    2018-01-01

    As a promising photodynamic therapy (PDT) agent, Al(III) phthalocyanine chloride tetrasulfonic acid (AlPcS 4 ) provides deep penetration into tissue, high quantum yields, good photostability, and low photobleaching. However, its low delivery efficiency and high binding affinity to serum albumin cause its low penetration into cancer cells, further limiting its PDT effect on gastric cancer. In order to improve AlPcS 4 /PDT effect, the AlPcS 4 delivery sys tems with different drug carriers were synthesized and investigated. Gold nanorods, cationic liposomes, and Pluronic ® F127 nanomicellars were used to formulate the AlPcS 4 delivery systems. The anticancer effect was evaluated by CCK-8 assay and colony formation assay. The delivery efficiency of AlPcS 4 and the binding affinity to serum proteins were determined by fluorescence intensity assay. The apoptosis and necrosis ability, reactive oxygen species and singlet oxygen generation, mitochondrial transmembrane potential and ([Ca 2+ ] i ) concentration were further measured to evaluate the mechanism of cell death. The series of synthesized AlPcS 4 delivery systems with different drug carriers improve the limited PDT effect in varying degrees. In contrast, AlPcS 4 complex with gold nanorods has significant anticancer effects because gold nanorods are not only suitable for AlPcS 4 delivery, but also exhibit enhanced singlet oxygen generation effect and photothermal effect to induce cell death directly. Moreover, AlPcS 4 complex with cationic liposomes shows the potent inhibition effect because of its optimal AlPcS 4 delivery efficiency and ability to block serum albumin. In addition, AlPcS 4 complex with Pluronic F127 exhibits inferior PDT effect but presents lower cytotoxicity, slower dissociation rate, and longer retention time of incorporated drugs; thus, F127-AlPcS 4 is used for prolonged gastric cancer therapy. The described AlPcS 4 drug delivery systems provide promising agents for gastric cancer therapy.

  13. Assessing the sensitivity of benzene cluster cation chemical ionization mass spectrometry toward a wide array of biogenic volatile organic compounds

    Science.gov (United States)

    Lavi, Avi; Vermeuel, Michael; Novak, Gordon; Bertram, Timothy

    2017-04-01

    Chemical ionization mass spectrometry is a real-time, sensitive and selective measurement technique for the detection of volatile organic compounds (VOCs). The benefits of CIMS technology make it highly suitable for field measurements that requires fast (10Hz and higher) response rates, such as the study of surface-atmosphere exchange processes by the eddy covariance method. The use of benzene cluster cations as a regent ion was previously demonstrated as a sensitive and selective method for the detection of select biogenic VOCs (e.g. isoprene, monoterpenes and sesquiterpenes) [Kim et al., 2016; Leibrock and Huey, 2000]. Quantitative analysis of atmospheric trace gases necessitates calibration for each analyte as a function of atmospheric conditions. We describe a custom designed calibration system, based on liquid evaporation, for determination of the sensitivity of the benzene-CIMS to a wide range of organic compounds at atmospherically relevant mixing ratios (volatile organic compounds, Atmos Meas Tech, 9(4), 1473-1484, doi:10.5194/amt-9-1473-2016. Leibrock, E., and L. G. Huey (2000), Ion chemistry for the detection of isoprene and other volatile organic compounds in ambient air, Geophys Res Lett, 27(12), 1719-1722, doi:Doi 10.1029/1999gl010804.

  14. The nanocoherer: an electrically and mechanically resettable resistive switching device based on gold clusters assembled on paper

    Science.gov (United States)

    Minnai, Chloé; Mirigliano, Matteo; Brown, Simon A.; Milani, Paolo

    2018-03-01

    We report the realization of a resettable resistive switching device based on a nanostructured film fabricated by supersonic cluster beam deposition of gold clusters on plain paper substrates. Through the application of suitable voltage ramps, we obtain, in the same device, either a complex pattern of resistive switchings, or reproducible and stable switchings between low resistance and high resistance states, with an amplitude up to five orders of magnitude. Our device retains a state of internal resistance following the history of the applied voltage similar to that reported for memristors. The two different switching regimes in the same device are both stable, the transition between them is reversible, and it can be controlled by applying voltage ramps or by mechanical deformation of the substrate. The device behavior can be related to the formation, growth and breaking of junctions between the loosely aggregated gold clusters forming the nanostructured films. The fact that our cluster-assembled device is mechanically resettable suggests that it can be considered as the analog of the coherer: a switching device based on metallic powders used for the first radio communication system.

  15. Exploring the atomic structure of 1.8 nm monolayer-protected gold clusters with aberration-corrected STEM

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Jian; Jian, Nan; Ornelas, Isabel; Pattison, Alexander J. [Nanoscale Physics Research Laboratory, School of Physics and Astronomy, University of Birmingham, Birmingham B15 2TT (United Kingdom); Lahtinen, Tanja; Salorinne, Kirsi [Department of Chemistry, Nanoscience Center, University of Jyväskylä, FI-40014 Jyväskylä (Finland); Häkkinen, Hannu [Department of Chemistry, Nanoscience Center, University of Jyväskylä, FI-40014 Jyväskylä (Finland); Department of Physics, Nanoscience Center, University of Jyväskylä, FI-40014 Jyväskylä (Finland); Palmer, Richard E., E-mail: richardepalmerwork@yahoo.com [Nanoscale Physics Research Laboratory, School of Physics and Astronomy, University of Birmingham, Birmingham B15 2TT (United Kingdom)

    2017-05-15

    Monolayer-protected (MP) Au clusters present attractive quantum systems with a range of potential applications e.g. in catalysis. Knowledge of the atomic structure is needed to obtain a full understanding of their intriguing physical and chemical properties. Here we employed aberration-corrected scanning transmission electron microscopy (ac-STEM), combined with multislice simulations, to make a round-robin investigation of the atomic structure of chemically synthesised clusters with nominal composition Au{sub 144}(SCH{sub 2}CH{sub 2}Ph){sub 60} provided by two different research groups. The MP Au clusters were “weighed” by the atom counting method, based on their integrated intensities in the high angle annular dark field (HAADF) regime and calibrated exponent of the Z dependence. For atomic structure analysis, we compared experimental images of hundreds of clusters, with atomic resolution, against a variety of structural models. Across the size range 123–151 atoms, only 3% of clusters matched the theoretically predicted Au{sub 144}(SR){sub 60} structure, while a large proportion of the clusters were amorphous (i.e. did not match any model structure). However, a distinct ring-dot feature, characteristic of local icosahedral symmetry, was observed in about 20% of the clusters. - Highlights: • Chemically synthesised gold clusters were “weighed” by atom counting to get true size. • Image simulations show a few percent of clusters have the predicted atomic structure. • But a specific ring-dot feature indicates local icosahedral order in many clusters.

  16. A new route to gold nanoflowers

    Science.gov (United States)

    Liebig, Ferenc; Henning, Ricky; Sarhan, Radwan M.; Prietzel, Claudia; Bargheer, Matias; Koetz, Joachim

    2018-05-01

    Catanionic vesicles spontaneously formed by mixing the anionic surfactant bis(2-ethylhexyl) sulfosuccinate sodium salt with the cationic surfactant cetyltrimethylammonium bromide were used as a reducing medium to produce gold clusters, which are embedded and well-ordered into the template phase. The gold clusters can be used as seeds in the growth process that follows by adding ascorbic acid as a mild reducing component. When the ascorbic acid was added very slowly in an ice bath round-edged gold nanoflowers were produced. When the same experiments were performed at room temperature in the presence of Ag+ ions, sharp-edged nanoflowers could be synthesized. The mechanism of nanoparticle formation can be understood to be a non-diffusion-limited Ostwald ripening process of preordered gold nanoparticles embedded in catanionic vesicle fragments. Surface-enhanced Raman scattering experiments show an excellent enhancement factor of 1.7 · 105 for the nanoflowers deposited on a silicon wafer.

  17. A comparison of three clustering methods for finding subgroups in MRI, SMS or clinical data: SPSS TwoStep Cluster analysis, Latent Gold and SNOB.

    Science.gov (United States)

    Kent, Peter; Jensen, Rikke K; Kongsted, Alice

    2014-10-02

    There are various methodological approaches to identifying clinically important subgroups and one method is to identify clusters of characteristics that differentiate people in cross-sectional and/or longitudinal data using Cluster Analysis (CA) or Latent Class Analysis (LCA). There is a scarcity of head-to-head comparisons that can inform the choice of which clustering method might be suitable for particular clinical datasets and research questions. Therefore, the aim of this study was to perform a head-to-head comparison of three commonly available methods (SPSS TwoStep CA, Latent Gold LCA and SNOB LCA). The performance of these three methods was compared: (i) quantitatively using the number of subgroups detected, the classification probability of individuals into subgroups, the reproducibility of results, and (ii) qualitatively using subjective judgments about each program's ease of use and interpretability of the presentation of results.We analysed five real datasets of varying complexity in a secondary analysis of data from other research projects. Three datasets contained only MRI findings (n = 2,060 to 20,810 vertebral disc levels), one dataset contained only pain intensity data collected for 52 weeks by text (SMS) messaging (n = 1,121 people), and the last dataset contained a range of clinical variables measured in low back pain patients (n = 543 people). Four artificial datasets (n = 1,000 each) containing subgroups of varying complexity were also analysed testing the ability of these clustering methods to detect subgroups and correctly classify individuals when subgroup membership was known. The results from the real clinical datasets indicated that the number of subgroups detected varied, the certainty of classifying individuals into those subgroups varied, the findings had perfect reproducibility, some programs were easier to use and the interpretability of the presentation of their findings also varied. The results from the artificial datasets

  18. Metal Enhanced Fluorescence on Super-Hydrophobic Clusters of Gold Nanoparticles

    KAUST Repository

    Battista, Edmondo; Coluccio, Maria Laura; Alabastri, Alessandro; Barberio, Marianna; Causa, Filippo; Netti, Paolo Antonio; Di Fabrizio, Enzo M.; Gentile, Francesco

    2016-01-01

    We used optical lithography, electroless deposition and deep reactive ion etching techniques to realize arrays of super-hydrophobic gold nanoparticles arranged in a hierarchical structure. At the micro-scale, silicon-micro pillars in the chip permit to manipulate and concentrate biological solutions, at the nano-scale, gold nanoparticles enable metal enhanced fluorescence (MEF) effects, whereby fluorescence signal of fluorophores in close proximity to a rough metal surface is amplified by orders of magnitude. Here, we demonstrated the device in the analysis of fluorescein derived gold-binding peptides (GBP-FITC). While super-hydrophobic schemes and MEF effects have been heretofore used in isolation, their integration in a platform may advance the current state of fluorescence-based sensing technology in medical diagnostics and biotechnology. This scheme may be employed in protein microarrays where the increased sensitivity of the device may enable the early detection of cancer biomarkers or other proteins of biomedical interest.

  19. Metal Enhanced Fluorescence on Super-Hydrophobic Clusters of Gold Nanoparticles

    KAUST Repository

    Battista, Edmondo

    2016-12-15

    We used optical lithography, electroless deposition and deep reactive ion etching techniques to realize arrays of super-hydrophobic gold nanoparticles arranged in a hierarchical structure. At the micro-scale, silicon-micro pillars in the chip permit to manipulate and concentrate biological solutions, at the nano-scale, gold nanoparticles enable metal enhanced fluorescence (MEF) effects, whereby fluorescence signal of fluorophores in close proximity to a rough metal surface is amplified by orders of magnitude. Here, we demonstrated the device in the analysis of fluorescein derived gold-binding peptides (GBP-FITC). While super-hydrophobic schemes and MEF effects have been heretofore used in isolation, their integration in a platform may advance the current state of fluorescence-based sensing technology in medical diagnostics and biotechnology. This scheme may be employed in protein microarrays where the increased sensitivity of the device may enable the early detection of cancer biomarkers or other proteins of biomedical interest.

  20. Monoatomic and cluster beam effect on ToF-SIMS spectra of self-assembled monolayers on gold

    Energy Technology Data Exchange (ETDEWEB)

    Tuccitto, N. [Dipartimento di Scienze Chimiche Universita degli Studi di Catania, v.le A. Doria 6, 95125, Catania (Italy)], E-mail: n.tuccitto@unict.it; Torrisi, V.; Delfanti, I.; Licciardello, A. [Dipartimento di Scienze Chimiche Universita degli Studi di Catania, v.le A. Doria 6, 95125, Catania (Italy)

    2008-12-15

    Self-assembled monolayers represent well-defined systems that is a good model surface to study the effect of primary ion beams used in secondary ion mass spectrometry. The effect of polyatomic primary beams on both aliphatic and aromatic self-assembled monolayers has been studied. In particular, we analysed the variation of the relative secondary ion yield of both substrate metal-cluster (Au{sub n}{sup -}) in comparison with the molecular ions (M{sup -}) and clusters (M{sub x}Au{sub y}{sup -}) by using Bi{sup +}, Bi{sub 3}{sup +}, Bi{sub 5}{sup +} beams. Moreover, the differences in the secondary ion generation efficiency are discussed. The main effect of the cluster beams is related to an increased formation of low-mass fragments and to the enhancement of the substrate related gold-clusters. The results show that, at variance of many other cases, the static SIMS of self-assembled monolayers does not benefit of the use of polyatomic primary ions.

  1. Macrocluster desorption effect caused by single MCI: charges of gold clusters (2-20 nm) desorbed due to electronic processes induced by fission fragment bombardment in nanodispersed gold targets

    International Nuclear Information System (INIS)

    Baranov, I.; Jarmiychuk, S.; Kirillov, S.; Novikov, A.; Obnorskii, V.; Pchelintsev, A.; Wien, K.; Reimann, C.

    1999-01-01

    In this work the charge state of the negatively charged gold nanocluster ions (2-20 nm) that were desorbed from nanodispersed gold islet targets by 252 Cf fission fragments via electronic processes is studied. Mean cluster charge was calculated as a ratio of mean cluster mass to mean mass-to-charge ratio . Cluster masses were measured by means of a collector technique employing transmission electron microscopy and scanning force microscopy, while m/q was measured by means of a tandem TOF-spectrometer. It is shown that the nanocluster ions are mostly multiply charged (2-16e) and the charge increases non-linearly with the cluster size. The results are discussed

  2. Systematic Study of Au6 to Au12 Gold Clusters on MgO(100) F Centers Using Density-Functional Theory

    DEFF Research Database (Denmark)

    Vilhelmsen, Lasse; Hammer, Bjørk

    2012-01-01

    We present an optimized genetic algorithm used in conjunction with density-functional theory in the search for stable gold clusters and O2 adsorption ensembles in F centers at MgO(100). For Au8 the method recovers known structures and identifies several more stable ones. When O2 adsorption...

  3. Bi-Directional Ion Emission from Massive Gold Cluster Impacts on Nanometric Carbon Foils.

    Science.gov (United States)

    Debord, J Daniel; Della-Negra, Serge; Fernandez-Lima, Francisco A; Verkhoturov, Stanislav V; Schweikert, Emile A

    2012-04-12

    Carbon cluster emission from thin carbon foils (5-40 nm) impacted by individual Au(n) (+q) cluster projectiles (95-125 qkeV, n/q = 3-200) reveals features regarding the energy deposition, projectile range, and projectile fate in matter as a function of the projectile characteristics. For the first time, the secondary ion emission from thin foils has been monitored simultaneously in both forward and backward emission directions. The projectile range and depth of emission were examined as a function of projectile size, energy, and target thickness. A key finding is that the massive cluster impact develops very differently from that of a small polyatomic projectile. The range of the 125 qkeV Au(100q) (+q) (q ≈ 4) projectile is estimated to be 20 nm (well beyond the range of an equal velocity Au(+)) and projectile disintegration occurs at the exit of even a 5 nm thick foil.

  4. Giant metal sputtering yields induced by 20-5000 keV/atom gold clusters

    International Nuclear Information System (INIS)

    Andersen, H.H.; Brunelle, A.; Della-Negra, S.; Depauw, J.; Jacquet, D.; Le Beyec, Y.

    1997-01-01

    Very large non-linear effects have been found in cluster-induced metal sputtering over a broad projectile energy interval for the first time. Recently available cluster beams from tandem accelerators have allowed sputtering yield measurements to be made with Au 1 to Au 5 from 20 keV/atom to 5 MeV/atom. The cluster-sputtering yield maxima were found at the same total energy but not at the same energy/atom as expected. For Au 5 a yield as high as 3000 was reached at 150 keV/atom while the Au 1 yield was only 55 at the same velocity. The Sigmund-Claussen thermal spike theory, which fits published data at low energy, cannot reproduce our extended new data set. (author)

  5. Contributions of distinct gold species to catalytic reactivity for carbon monoxide oxidation

    Science.gov (United States)

    Guo, Li-Wen; Du, Pei-Pei; Fu, Xin-Pu; Ma, Chao; Zeng, Jie; Si, Rui; Huang, Yu-Ying; Jia, Chun-Jiang; Zhang, Ya-Wen; Yan, Chun-Hua

    2016-11-01

    Small-size (carbon monoxide at room temperature, by the aid of in situ X-ray absorption fine structure analysis and in situ diffuse reflectance infrared Fourier transform spectroscopy. We find that the metallic gold component in clusters or particles plays a much more critical role as the active site than the cationic single-atom gold species for the room-temperature carbon monoxide oxidation reaction.

  6. Bi-Directional Ion Emission from Massive Gold Cluster Impacts on Nanometric Carbon Foils

    OpenAIRE

    DeBord, J. Daniel; Della-Negra, Serge; Fernandez-Lima, Francisco A.; Verkhoturov, Stanislav V.; Schweikert, Emile A.

    2012-01-01

    Carbon cluster emission from thin carbon foils (5–40 nm) impacted by individual Aun+q cluster projectiles (95–125 qkeV, n/q = 3–200) reveals features regarding the energy deposition, projectile range, and projectile fate in matter as a function of the projectile characteristics. For the first time, the secondary ion emission from thin foils has been monitored simultaneously in both forward and backward emission directions. The projectile range and depth of emission were examined as a function...

  7. Geometric, stability, and electronic properties of gold-doped Pd clusters (Pd{sub n}Au, n = 3~20)

    Energy Technology Data Exchange (ETDEWEB)

    Huan, Hao; Chen, Yan; Wang, Tao; Ye, Xiang, E-mail: yexiang@shnu.edu.cn [Shanghai Normal University, Department of Physics (China); Gu, Xiao, E-mail: gx@cqu.edu.cn [Chongqing University, Department of Applied Physics (China)

    2016-11-15

    The structure, stability, and electronic properties of Pd{sub n}Au (n = 3~20) clusters are studied by density functional theory. The results show that the clusters studied here prefer three-dimensional structures even with very small atom number. It is found that the binding energies of Pd{sub n}Au clusters are higher than the corresponding pure Pd{sub n} clusters with the same atom number. Most Pd{sub n}Au clusters studied here are magnetic with magnetic moments ranging from 1.0 to 7.0 μ{sub B.} The dissociation energies of Pd atoms are lower than the doped gold atom, that is the doped Au atom will increase the mother clusters stability and activity.

  8. Assessment of interaction-strength interpolation formulas for gold and silver clusters

    Science.gov (United States)

    Giarrusso, Sara; Gori-Giorgi, Paola; Della Sala, Fabio; Fabiano, Eduardo

    2018-04-01

    The performance of functionals based on the idea of interpolating between the weak- and the strong-interaction limits the global adiabatic-connection integrand is carefully studied for the challenging case of noble-metal clusters. Different interpolation formulas are considered and various features of this approach are analyzed. It is found that these functionals, when used as a correlation correction to Hartree-Fock, are quite robust for the description of atomization energies, while performing less well for ionization potentials. Future directions that can be envisaged from this study and a previous one on main group chemistry are discussed.

  9. Gold atoms and clusters on MgO(100) films; an EPR and IRAS study

    Science.gov (United States)

    Yulikov, M.; Sterrer, M.; Risse, T.; Freund, H.-J.

    2009-06-01

    Single gold atoms deposited on single crystalline MgO(1 0 0) films grown on Mo(1 0 0) are characterized by electron paramagnetic resonance spectroscopy as well as IR spectroscopy using CO as probe molecules. In this article we describe the first angular dependent measurements to determine the principal hyperfine components of a secondary hyperfine interaction, namely, with 17O of the MgO. The values determined here are in perfect agreement with theoretical expectations and corroborate the previously reported binding mechanism of Au atoms on the oxygen anions of the MgO terrace. The temperature dependent EPR data reveal an onset of Au atom mobility at about 80 K while the formation of Au particles occurs only above 125 K. By an analysis of the EPR line width in combination with STM measurements it is possible to deduce an increase of the interatomic distance above 80 K. The Au/CO complexes show a somewhat smaller temperature stability as compared to the Au atoms. The observed thermal stability is in perfect agreement with theoretical predictions for CO desorption.

  10. Is the largest aqueous gold cluster a superatom complex? Electronic structure & optical response of the structurally determined Au146(p-MBA)57.

    Science.gov (United States)

    López-Lozano, Xóchitl; Plascencia-Villa, G; Calero, G; Whetten, R L; Weissker, Hans-Christian

    2017-12-07

    The new water-soluble gold cluster Au 146 (p-MBA) 57 , the structure of which has been recently determined at sub-atomic resolution by Vergara et al., is the largest aqueous gold cluster ever structurally determined and likewise the smallest cluster with a stacking fault. The core presents a twinned truncated octahedron, while additional peripheral gold atoms follow a C 2 rotational symmetry. According to the usual counting rules of the superatom complex (SAC) model, the compound attains a number of 92 SAC electrons if the overall net charge is 3- (three additional electrons). As this is the number of electrons required for a major shell closing, the question arises of whether Au 146 (p-MBA) 57 should be regarded as a superatom complex. Starting from the experimental coordinates we have analyzed the structure using density-functional theory. The optimized (relaxed) structure retains all the connectivity of the experimental coordinates, while removing much of its irregularities in interatomic distances, thereby enhancing the C 2 -symmetry feature. On analyzing the angular-momentum-projected states, we show that, despite a small gap, the electronic structure does not exhibit SAC model character. In addition, optical absorption spectra are found to be relatively smooth compared to the example of the Au 144 (SR) 60 cluster. The Au 146 (SR) 57 does not derive its stability from SAC character; it cannot be considered as a superatom complex.

  11. Actinide cation-cation complexes

    International Nuclear Information System (INIS)

    Stoyer, N.J.; Seaborg, G.T.

    1994-12-01

    The +5 oxidation state of U, Np, Pu, and Am is a linear dioxo cation (AnO 2 + ) with a formal charge of +1. These cations form complexes with a variety of other cations, including actinide cations. Other oxidation states of actinides do not form these cation-cation complexes with any cation other than AnO 2 + ; therefore, cation-cation complexes indicate something unique about AnO 2 + cations compared to actinide cations in general. The first cation-cation complex, NpO 2 + ·UO 2 2+ , was reported by Sullivan, Hindman, and Zielen in 1961. Of the four actinides that form AnO 2 + species, the cation-cation complexes of NpO 2 + have been studied most extensively while the other actinides have not. The only PuO 2 + cation-cation complexes that have been studied are with Fe 3+ and Cr 3+ and neither one has had its equilibrium constant measured. Actinides have small molar absorptivities and cation-cation complexes have small equilibrium constants; therefore, to overcome these obstacles a sensitive technique is required. Spectroscopic techniques are used most often to study cation-cation complexes. Laser-Induced Photacoustic Spectroscopy equilibrium constants for the complexes NpO 2 + ·UO 2 2+ , NpO 2 + ·Th 4+ , PuO 2 + ·UO 2 2+ , and PuO 2 + ·Th 4+ at an ionic strength of 6 M using LIPAS are 2.4 ± 0.2, 1.8 ± 0.9, 2.2 ± 1.5, and ∼0.8 M -1

  12. Gold chloride clusters with Au(III) and Au(I) probed by FT-ICR mass spectrometry and MP2 theory.

    Science.gov (United States)

    Lemke, Kono H

    2014-05-07

    Microsolvated clusters of gold chloride are probed by electrospray ionization mass spectrometry (ESI-MS) and scalar relativistic electronic structure calculations. Electrospray ionization of aqueous AuCl3 leads to mononuclear clusters of types [AuCl2](+)(H2O)n (n = 0-4), [AuOHCl](+)(H2O)n (n = 0-1) and [AuCl2](+)(HCl)2(H2O)n (n = 0-4). In addition, strong ion signals due to dinuclear [Au2Cl5-xOHx](+)(H2O)n (x = 0-1) are present in ESI mass spectra of aqueous AuCl3, with the abundance of individual dinuclear species controlled by the concentration-dependent variation of the precursor complexes [AuCl2-xOHx](+)(H2O)n and AuCl3. Equilibrium structures, energies and thermodynamic properties of mono- and dinuclear gold clusters have been predicted using MP2 and CCSD(T) theory, and these data have been applied to examine the influence of microsolvation on cluster stability. Specifically, results from CCSD(T) calculations indicate that non-covalently bound ion-neutral complexes Au(+)(Cl2)(H2O)n, with formal Au(I), are the dominant forms of mononuclear gold with n = 0-2, while higher hydrates (n > 2) are covalently bound [AuCl2](+)(H2O)n complexes in which gold exists as Au(III). MP2 calculations show that the lowest energy structure of dinuclear gold is an ion-molecule cluster [Au2Cl(Cl2)2](+) consisting of a single-bridged digold-chloronium ion bound end-on to two dichlorine ligands, with two higher energy isomers, single-bridged [Au2Cl3(Cl2)](+) and double-bridged [Au2Cl5](+) clusters. Finally, AuAu interactions in the singly-bridged clusters [Au2Cl(Cl2)2](+)(H2O)n and [Au2Cl3(Cl2)](+)(H2O)n are examined employing a wide range of computational tools, including natural bond order (NBO) analysis and localized orbital locator (LOL) profiles.

  13. Ferric hydroxide supported gold subnano clusters or quantum dots: enhanced catalytic performance in chemoselective hydrogenation.

    Science.gov (United States)

    Liu, Lequan; Qiao, Botao; Ma, Yubo; Zhang, Juan; Deng, Youquan

    2008-05-21

    An attempt to prepare ferric hydroxide supported Au subnano clusters via modified co-precipitation without any calcination was made. High resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) have been employed to study the structure and chemical states of these catalysts. No Au species could be observed in the HRTEM image nor from the XRD pattern, suggesting that the sizes of the Au species in and on the ferric hydroxide support were less than or around 1 nm. Chemoselective hydrogenation of aromatic nitro compounds and alpha,beta-unsaturated aldehydes was selected as a probe reaction to examine the catalytic properties of this catalyst. Under the same reaction conditions, such as 100 degrees C and 1 MPa H2 in the hydrogenation of aromatic nitro compounds, a 96-99% conversion (except for 4-nitrobenzonitrile) with 99% selectivity was obtained over the ferric hydroxide supported Au catalyst, and the TOF values were 2-6 times higher than that of the corresponding ferric oxide supported catalyst with 3-5 nm size Au particles. For further evaluation of this Au catalyst in the hydrogenation of citral and cinnamaldehyde, selectivity towards unsaturated alcohols was 2-20 times higher than that of the corresponding ferric oxide Au catalyst.

  14. Protein-gold clusters-capped mesoporous silica nanoparticles for high drug loading, autonomous gemcitabine/doxorubicin co-delivery, and in-vivo tumor imaging

    KAUST Repository

    Croissant, Jonas G.; Zhang, Dingyuan; Alsaiari, Shahad K.; Lu, Jie; Deng, Lin; Tamanoi, Fuyuhiko; Zink, Jeffrey I.; Khashab, Niveen M.

    2016-01-01

    Functional nanocarriers capable of transporting high drug contents without premature leakage and to controllably deliver several drugs are needed for better cancer treatments. To address this clinical need, gold cluster bovine serum albumin (AuNC@BSA) nanogates were engineered on mesoporous silica nanoparticles (MSN) for high drug loadings and co-delivery of two different anticancer drugs. The first drug, gemcitabine (GEM, 40 wt%), was loaded in positively-charged ammonium-functionalized MSN (MSN-NH3+). The second drug, doxorubicin (DOX, 32 wt%), was bound with negatively-charged AuNC@BSA electrostatically-attached onto MSN-NH3+, affording highly loaded pH-responsive MSN-AuNC@BSA nanocarriers. The co-delivery of DOX and GEM was achieved for the first time via an inorganic nanocarrier, possessing a zero-premature leakage behavior as well as drug loading capacities seven times higher than polymersome NPs. Besides, unlike the majority of strategies used to cap the pores of MSN, AuNC@BSA nanogates are biotools and were applied for targeted red nuclear staining and in-vivo tumor imaging. The straightforward non-covalent combination of MSN and gold-protein cluster bioconjugates thus leads to a simple, yet multifunctional nanotheranostic for the next generation of cancer treatments.

  15. Protein-gold clusters-capped mesoporous silica nanoparticles for high drug loading, autonomous gemcitabine/doxorubicin co-delivery, and in-vivo tumor imaging

    KAUST Repository

    Croissant, Jonas G.

    2016-03-23

    Functional nanocarriers capable of transporting high drug contents without premature leakage and to controllably deliver several drugs are needed for better cancer treatments. To address this clinical need, gold cluster bovine serum albumin (AuNC@BSA) nanogates were engineered on mesoporous silica nanoparticles (MSN) for high drug loadings and co-delivery of two different anticancer drugs. The first drug, gemcitabine (GEM, 40 wt%), was loaded in positively-charged ammonium-functionalized MSN (MSN-NH3+). The second drug, doxorubicin (DOX, 32 wt%), was bound with negatively-charged AuNC@BSA electrostatically-attached onto MSN-NH3+, affording highly loaded pH-responsive MSN-AuNC@BSA nanocarriers. The co-delivery of DOX and GEM was achieved for the first time via an inorganic nanocarrier, possessing a zero-premature leakage behavior as well as drug loading capacities seven times higher than polymersome NPs. Besides, unlike the majority of strategies used to cap the pores of MSN, AuNC@BSA nanogates are biotools and were applied for targeted red nuclear staining and in-vivo tumor imaging. The straightforward non-covalent combination of MSN and gold-protein cluster bioconjugates thus leads to a simple, yet multifunctional nanotheranostic for the next generation of cancer treatments.

  16. Au70S20(PPh3)12: an intermediate sized metalloid gold cluster stabilized by the Au4S4 ring motif and Au-PPh3 groups.

    Science.gov (United States)

    Kenzler, Sebastian; Schrenk, Claudio; Frojd, Andrew R; Häkkinen, Hannu; Clayborne, Andre Z; Schnepf, Andreas

    2018-01-02

    Reducing (Ph 3 P)AuSC(SiMe 3 ) 3 with l-Selectride® gives the medium-sized metalloid gold cluster Au 70 S 20 (PPh 3 ) 12 . Computational studies show that the phosphine bound Au-atoms not only stabilize the electronic structure of Au 70 S 20 (PPh 3 ) 12 , but also behave as electron acceptors leading to auride-like gold atoms on the exterior.

  17. Flow cytometry with gold nanoparticlesand their clusters as scattering contrast agents: FDTD simulation of light-cell interaction

    DEFF Research Database (Denmark)

    Tanev, Stoyan; Sun, Wenbo; Pond, James

    2009-01-01

    refractive index matching conditions and by cells labeled by gold nanoparticles. The optical schematics including phase contrast (OPCM) microscopy as a prospective modality for in vivo flow cytometry is also analyzed. The validation of the FDTD approach for the simulation of flow cytometry may open a new...

  18. clusters

    Indian Academy of Sciences (India)

    2017-09-27

    Sep 27, 2017 ... Author for correspondence (zh4403701@126.com). MS received 15 ... lic clusters using density functional theory (DFT)-GGA of the DMOL3 package. ... In the process of geometric optimization, con- vergence thresholds ..... and Postgraduate Research & Practice Innovation Program of. Jiangsu Province ...

  19. clusters

    Indian Academy of Sciences (India)

    environmental as well as technical problems during fuel gas utilization. ... adsorption on some alloys of Pd, namely PdAu, PdAg ... ried out on small neutral and charged Au24,26,27, Cu,28 ... study of Zanti et al.29 on Pdn (n = 1–9) clusters.

  20. Combined Experimental and Theoretical DFT Study of Molecular Nanowires Negative Differential Resistance and Interaction With Gold Clusters

    Czech Academy of Sciences Publication Activity Database

    Záliš, Stanislav; Kratochvílová, Irena; Zambova, A.; Mbindyo, J.; Mallouk, T. E.; Mayer, T. S.

    2005-01-01

    Roč. 18, č. 2 (2005), s. 201-206 ISSN 1292-8941 R&D Projects: GA AV ČR 1ET400400413; GA AV ČR IAA400400501 Institutional research plan: CEZ:AV0Z40400503; CEZ:AV0Z10100520 Keywords : molecule/gold transport interfaces * single molecules * metal nanowires * junctions Subject RIV: CG - Electrochemistry Impact factor: 2.503, year: 2005

  1. Evaluation of secondary ion yield enhancement from polymer material by using TOF-SIMS equipped with a gold cluster ion source

    Energy Technology Data Exchange (ETDEWEB)

    Aimoto, K. [Department of Applied Physics, Faculty of Engineering, Seikei University, 3-3-1 Kichijioji-Kitamachi, Musashino-shi, Tokyo 180-8633 (Japan)]. E-mail: dm053502@cc.seikei.ac.jp; Aoyagi, S. [Department of Regional Development, Faculty of Life and Environmental Science, Shimane University, 1060 Nishikawatsu-cho, Matsue-shi, Shimane 690-8504 (Japan); Kato, N. [Department of Applied Physics, Faculty of Engineering, Seikei University, 3-3-1 Kichijioji-Kitamachi, Musashino-shi, Tokyo 180-8633 (Japan); Iida, N. [ULVAC-PHI, Inc., 370 Enzo, Chigasaki, Kanagawa 253-0084 (Japan); Yamamoto, A. [ULVAC-PHI, Inc., 370 Enzo, Chigasaki, Kanagawa 253-0084 (Japan); Kudo, M. [Department of Applied Physics, Faculty of Engineering, Seikei University, 3-3-1 Kichijioji-Kitamachi, Musashino-shi, Tokyo 180-8633 (Japan)

    2006-07-30

    We investigated the enhancement of the secondary ion intensity in the TOF-SIMS spectra obtained by Au{sup +} and Au{sub 3} {sup +} bombardment in comparison with Ga{sup +} excitation using polymer samples with different molecular weight distributions. Since the polymer samples used in this experiment have a wide molecular weight distribution, the advantages of the gold cluster primary ion source over monoatomic ion could accurately be evaluated. It was observed that the degree of fragmentation decreased by the usage of cluster primary ion beam compared with monoatomic ion beam, which was observed as a shift of the intensity distribution in the spectra. It was also found out that the mass effect of Au{sup +} and Ga{sup +} as monoatomic primary ion, resulted in about 10-60 times of enhancement for both samples with different molecular distributions. On the other hand, the Au{sub 3} {sup +} bombardment caused intensity enhancement about 100-2600 compared with Ga{sup +} bombardment, depending on the mass range of the detected secondary ion species. The cluster primary ion effect of Au{sub 3} {sup +}, compared with Au{sup +}, therefore, was estimated to be about 10-45.

  2. Synthesis of highly fluorescent and thio-linkers stabilize gold quantum dots and nano clusters in DMF for bio-labeling

    Energy Technology Data Exchange (ETDEWEB)

    Rastogi, Shiva K., E-mail: srastogi@uidaho.edu [University of Idaho, Department of Chemistry (United States); Denn, Benjamin D.; Branen, A. Larry [University of Idaho, Coeur D' Alene, Biosensors and Nanotechnology Application Laboratory (BNAL) (United States)

    2012-01-15

    This study demonstrates a one versus two-step synthesis of fluorescent gold quantum dots (F-AuQDs) and nano clusters (F-AuNCs) functionalized with thiolated organic linkers using reduction of gold precursor in N,N Prime -dimethylformamide in 1 h of reaction. The F-AuQDs and F-AuNCs show fluorescence emission at 425 {+-} 5 nm upon excitation at 345 {+-} 5 nm of wavelength, with good water solubility and stability. Five different thiolated organic binary linkers consisting of various functional groups including: carboxylic acid, hydroxyl, and aromatic amine, were conjugated with the F-AuQDs and F-AuNCs. The formation mechanism and functionalization of the F-AuQDs and F-AuNCs was characterized using UV-vis absorption spectra, UV-vis light, fluorescent emission spectra, pH, TEM, and FTIR. The fluorescence emission of the F-AuQDs and F-AuNCs is greatly dependent on the thio-linker. This novel one-step approach provides facile and fast synthesis of F-AuQDs and F-AuNCs over the two-step method, with less than 5 h of reaction and workup compared to more than 28 h of reaction for the two-step approach. These thio-linker functionalized F-AuQDs and F-AuNCs have a wide application in fluorescent labeling of biomolecules, optical devices, imaging, energy transfer, and biosensing.

  3. A phosphorescent silver(I)-gold (I) cluster complex that specifically lights up the nucleolus of living cells with FLIM imaging.

    Science.gov (United States)

    Chen, Min; Lei, Zhen; Feng, Wei; Li, Chunyan; Wang, Quan-Ming; Li, Fuyou

    2013-06-01

    The phosphorescent silver(I)-gold(I) cluster complex [CAu6Ag2(dppy)6](BF4)4 (N1) selectively stains the nucleolus, with a much lower uptake in the nucleus and cytoplasm, and exhibits excellent photostability. This Ag-Au cluster, which has a photoluminescent lifetime of microseconds, is particularly attractive as a probe in applications of time-gated microscopy. Investigation of the pathway of cellular entry indicated that N1 permeates the outer membrane and nuclear membrane of living cells through an energy-dependent and non-endocytic route within 10 min. High concentrations of N1 in the nucleolus have been quantified by inductively coupled plasma atomic emission spectroscopy (ICP-AES) and transmission electron microscopy coupled with an energy dispersive X-ray analysis (TEM-EDXA), which also helped to elucidate the mechanism of the specific staining. Intracellular selective staining may be correlated with the microenvironment of the nucleolus, which is consistent with experiments conducted at different phases of the cell cycle. These results prove that N1 is a very attractive phosphorescent staining reagent for visualizing the nucleolus of living cells. Copyright © 2013 Elsevier Ltd. All rights reserved.

  4. Flow cytometry with gold nanoparticles and their clusters as scattering contrast agents: FDTD simulation of light-cell interaction.

    Science.gov (United States)

    Tanev, Stoyan; Sun, Wenbo; Pond, James; Tuchin, Valery V; Zharov, Vladimir P

    2009-09-01

    The formulation of the finite-difference time-domain (FDTD) approach is presented in the framework of its potential applications to in-vivo flow cytometry based on light scattering. The consideration is focused on comparison of light scattering by a single biological cell alone in controlled refractive-index matching conditions and by cells labeled by gold nanoparticles. The optical schematics including phase contrast (OPCM) microscopy as a prospective modality for in-vivo flow cytometry is also analyzed. The validation of the FDTD approach for the simulation of flow cytometry may open up a new avenue in the development of advanced cytometric techniques based on scattering effects from nanoscale targets. 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

  5. Monolayer-protected clusters of gold nanoparticles: impacts of stabilizing ligands on the heterogeneous electron transfer dynamics and voltammetric detection.

    Science.gov (United States)

    Pillay, Jeseelan; Ozoemena, Kenneth I; Tshikhudo, Robert T; Moutloali, Richard M

    2010-06-01

    Surface electrochemistry of novel monolayer-protected gold nanoparticles (MPCAuNPs) is described. Protecting ligands, (1-sulfanylundec-11-yl)tetraethylene glycol (PEG-OH) and (1-sulfanylundec-11-yl)poly(ethylene glycol)ic acid (PEG-COOH), of three different percent ratios (PEG-COOH:PEG-OH), 1:99 (MPCAuNP-COOH(1%)), 50:50 (MPCAuNP-COOH(50%)), and 99:1 (MPCAuNP-COOH(99%)), were studied. The electron transfer rate constants (k(et)/s(-1)) in organic medium decreased as the concentration of the surface-exposed -COOH group in the protecting monolayer ligand is increased: MPCAuNP-COOH(1%) (approximately 5 s(-1)) > MPCAuNP-COOH(50%) (approximately 4 s(-1)) > MPCAuNP-COOH(99%) (approximately 0.5 s(-1)). In aqueous medium, the trend is reversed. The surface pK(a) was estimated as approximately 8.2 for the MPCAuNP-COOH(1%), while both MPCAuNP-COOH(50%) and MPCAuNP-COOH(99%) showed two pK(a) values of about 5.0 and approximately 8.0. These results have been interpreted in terms of the quasi-solidity and quasi-liquidity of the terminal -OH and -COOH head groups, respectively. MPCAuNP-COOH(99%) excellently suppressed the voltammetric response of the ascorbic acid but enhanced the electrocatalytic detection of epinephrine compared to the other MPCAuNPs studied. This study reveals important factors that should be considered when designing electrode devices that employ monolayer-protected gold nanoparticles and possibly for some other redox-active metal nanoparticles.

  6. A novel colorimetric assay for rapid detection of cysteine and Hg²⁺ based on gold clusters.

    Science.gov (United States)

    Wang, Yi-Wei; Tang, Shurong; Yang, Huang-Hao; Song, Hongbo

    2016-01-01

    Inhibition and recovery of the catalytic activity of bovine serum albumin-capped gold nanoclusters (BSA-AuNCs) is observed for the first time by introduction of cysteine and Hg(2+). The prepared BSA-AuNCs possess highly intrinsic peroxidase-like activity. It can catalyze the oxidation of 3, 3, 5, 5-tetramethylbenzidine by H2O2 to produce a blue colored product. Based on this phenomenon, a new colorimetric assay for rapid, selective and sensitive detection of cysteine and Hg(2+) in aqueous solution has been demonstrated. The interaction process between target molecule and BSA-AuNCs is very fast, so that the whole test can be completed within ten minutes. Moreover, the fabricated colorimetric sensor is simple and cost-effective, without the need of nucleic acid based recognition element and complicated washing, separation and labeling process, thus holds great promise for routine analysis of cysteine and Hg(2+) in real samples. Copyright © 2015 Elsevier B.V. All rights reserved.

  7. Interaction of proteins with ionic liquid, alcohol and DMSO and in situ generation of gold nano-clusters in a cell.

    Science.gov (United States)

    Nandi, Somen; Parui, Sridip; Halder, Ritaban; Jana, Biman; Bhattacharyya, Kankan

    2018-06-01

    In this review, we give a brief overview on how the interaction of proteins with ionic liquids, alcohols and dimethyl sulfoxide (DMSO) influences the stability, conformational dynamics and function of proteins/enzymes. We present experimental results obtained from fluorescence correlation spectroscopy on the effect of ionic liquid or alcohol or DMSO on the size (more precisely, the diffusion constant) and conformational dynamics of lysozyme, cytochrome c and human serum albumin in aqueous solution. The interaction of ionic liquid with biomolecules (e.g. protein, DNA etc.) has emerged as a current frontier. We demonstrate that ionic liquids are excellent stabilizers of protein and DNA and, in some cases, cause refolding of a protein already denatured by chemical denaturing agents. We show that in ethanol-water binary mixture, proteins undergo non-monotonic changes in size and dynamics with increasing ethanol content. We also discuss the effect of water-DMSO mixture on the stability of proteins. We demonstrate how large-scale molecular dynamics simulations have revealed the molecular origin of this observed phenomenon and provide a microscopic picture of the immediate environment of the biomolecules. Finally, we describe how favorable interactions of ionic liquids may be utilized for in situ generation of fluorescent gold nano-clusters for imaging a live cell.

  8. Membrane Order Is a Key Regulator of Divalent Cation-Induced Clustering of PI(3,5)P2 and PI(4,5)P2

    Czech Academy of Sciences Publication Activity Database

    Sarmento, Maria Joäo; Coutinho, A.; Fedorov, A.; Prieto, M.; Fernandes, F.

    2017-01-01

    Roč. 33, č. 43 (2017), s. 12463-12477 ISSN 0743-7463 Institutional support: RVO:61388955 Keywords : cell membranes * fluorescence spectroscopy * cluster analysis Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 3.833, year: 2016

  9. Microsolvation of the acetanilide cation (AA(+)) in a nonpolar solvent: IR spectra of AA(+)-L(n) clusters (L = He, Ar, N2; n ≤ 10).

    Science.gov (United States)

    Schmies, Matthias; Patzer, Alexander; Schütz, Markus; Miyazaki, Mitsuhiko; Fujii, Masaaki; Dopfer, Otto

    2014-05-07

    Infrared photodissociation (IRPD) spectra of mass-selected cluster ions of acetanilide (N-phenylacetamide), AA(+)-Ln, with the ligands L = He (n = 1-2), Ar (n = 1-7), and N2 (n = 1-10) are recorded in the hydride stretch (amide A, νNH, νCH) and fingerprint (amide I-III) ranges of AA(+) in its (2)A'' ground electronic state. Cold AA(+)-Ln clusters are generated in an electron impact ion source, which predominantly produces the most stable isomer of a given cluster ion. Systematic vibrational frequency shifts of the N-H stretch fundamentals (νNH) provide detailed information about the sequential microsolvation process of AA(+) in a nonpolar (L = He and Ar) and quadrupolar (L = N2) solvent. In the most stable AA(+)-Ln clusters, the first ligand forms a hydrogen bond (H-bond) with the N-H proton of trans-AA(+) (t-AA(+)), whereas further ligands bind weakly to the aromatic ring (π-stacking). There is no experimental evidence for complexes with the less stable cis-AA(+) isomer. Quantum chemical calculations at the M06-2X/aug-cc-pVTZ level confirm the cluster growth sequence derived from the IR spectra. The calculated binding energies of De(H) = 720 and 1227 cm(-1) for H-bonded and De(π) = 585 and 715 cm(-1) for π-bonded Ar and N2 ligands in t-AA(+)-L are consistent with the observed photofragmentation branching ratios of AA(+)-Ln. Comparison between charged and neutral AA((+))-L dimers indicates that ionization switches the preferred ion-ligand binding motif from π-stacking to H-bonding. Electron removal from the HOMO of AA(+) delocalized over both the aromatic ring and the amide group significantly strengthens the C[double bond, length as m-dash]O bond and weakens the N-H bond of the amide group.

  10. Study on dependence of dose enhancement on cluster morphology of gold nanoparticles in radiation therapy using a body-centred cubic model

    Science.gov (United States)

    Ahn, Sang Hee; Chung, Kwangzoo; Shin, Jung Wook; Cheon, Wonjoong; Han, Youngyih; Park, Hee Chul; Choi, Doo Ho

    2017-10-01

    Gold nanoparticles (GNPs) injected in a body for dose enhancement in radiation therapy are known to form clusters. We investigated the dependence of dose enhancement on the GNP morphology using Monte-Carlo simulations and compared the model predictions with experimental data. The cluster morphology was approximated as a body-centred cubic (BCC) structure by placing GNPs at the 8 corners and the centre of a cube with an edge length of 0.22-1.03 µm in a 4  ×  4  ×  4 µm3 water-filled phantom. We computed the dose enhancement ratio (DER) for 50 and 260 kVp photons as a function of the distance from the cube centre for 12 different cube sizes. A 10 nm-wide concentric shell shaped detector was placed up to 100 nm away from a GNP at the cube centre. For model validation, simulations based on BCC and nanoparticle random distribution (NRD) models were performed using parameters that corresponded to the experimental conditions, which measured increases in the relative biological effect due to GNPs. We employed the linear quadratic model to compute cell surviving fraction (SF) and sensitizer enhancement ratio (SER). The DER is inversely proportional to the distance to the GNPs. The largest DERs were 1.97 and 1.80 for 50 kVp and 260 kVp photons, respectively. The SF predicted by the BCC model agreed with the experimental value within 10%, up to a 5 Gy dose, while the NRD model showed a deviation larger than 10%. The SERs were 1.21  ±  0.13, 1.16  ±  0.11, and 1.08  ±  0.11 according to the experiment, BCC, and NRD models, respectively. We most accurately predicted the GNP radiosensitization effect using the BCC approximation and suggest that the BCC model is effective for use in nanoparticle dosimetry.

  11. SU-F-T-661: Dependence of Gold Nano Particles Cluster Morphology On Dose Enhancement of Photon Radiation Therapy Apply for Radiation Biology Effect

    Energy Technology Data Exchange (ETDEWEB)

    Ahn, S [Department of Health Sciences and Technology, Samsung Advanced Institute for Health Sciences and Technology, Sungkyunkwan University (Korea, Republic of); Chung, K; Han, Y; Park, H [Samsung Medical Center, Sungkyunkwan University School of Medicine radiation oncology (Korea, Republic of)

    2016-06-15

    Purpose: Injected gold nano particles (GNPs) to a body for dose enhancement are known to form in the tumorcell cluster morphology. We investigated the dependence of dose enhancement on the morphology characteristic with an approximated morphology model by using Monte Carlo simulations. Methods: For MC simulation, TOPAS version 2.0P-03 was used. GNP cluster morphology was approximated as a body center cubic(BCC) model by placing 8 GNPs at the corner and one at the center of cube with length from 2.59 µm to 0.25 µm located in a 4 µm length water filled cube phantom. 4 µm length square shaped beams of poly-energetic 50, 260 kVp photons were irradiated to the water filled cube phantom with 100 nm diameter GNPs in it. Dose enhancement ratio(DER) was computed as a function of distance from the surface of the GNP at the cube center for 18 cubes geometries. For scoring particles, 10 nm width of concentric shell shaped detector was constructed up to 100 nm from the center. Total dose in a sphere of 100 nm radius of detector were normalized to 2.59 µm length cube morphology. To verified biological effect of BCC model applied to cell survival curve fitting. Results: DER increase as the distance of the GNPs reduces. DER was largest for 0.25 µm length cube. Dependence of GNP distance DER increment was 1.73, 1.60 for 50 kVp, 260 kVp photons, respectively. Also, Using BCC model applied to cell survival curve was well prediction. Conclusion: DER with GNPs was larger when they are closely packed in the phantom. Therefore, better therapeutic effects can be expected with close-packed GNPs. This research was supported by the NRF funded by the Ministry of Science, ICT & Future Planning (2012M3A9B6055201 and 2012R1A1A2042414), Samsung Medical Center grant[GFO1130081].

  12. Structure and bonding in gold compounds

    International Nuclear Information System (INIS)

    Parish, R.V.

    1988-01-01

    Recent developments in chemical applications of 197 Au Moessbauer spectroscopy are reviewed. For gold(I) and gold(III), systematic variations in isomer shift and quadrupole splitting are seen as the ligands are changed; the effects of change in coordination number of the gold atoms are also systematic. Data for gold(II) systems involving gold-gold bonds lie between those for corresponding gold(I) and gold(III) materials, showing a small increase in isomer shift and a larger increase in quadrupole splitting as the oxidation state decreases; these trends are explained in terms of the structures. Data for mixed-metal cluster compounds are much more sensitive to structural effects than in homonuclear clusters. Both sets of data show systematic changes with increase in the number of metal atoms to which the gold atom is bound. The connectivity also influences the recoil-free fraction. (orig.)

  13. Synthesis and Evaluation of Nanostructured Gold-Iron Oxide Catalysts for the Oxidative Dehydrogenation of Cyclohexane

    Science.gov (United States)

    Wu, Peng

    Shape-controlled iron oxide and gold-iron oxide catalysts with a cubic inverse spinel structure were studied in this thesis for the oxidative dehydrogenation of cyclohexane. The structure of iron oxide and gold-iron oxide catalysts has no major impact on their oxidative dehydrogenation activity. However, the product selectivity is influenced. Both cyclohexene and benzene are formed on bare iron oxide nanoshapes, while benzene is the only dehydrogenation product in the presence of gold. The selectivity of benzene over CO2 depends strongly on the stability of the iron oxide support and the gold-support interaction. The highest benzene yield has been observed on gold-iron oxide octahedra. {111}-bound nanooctahedra are highly stable in reaction conditions at 300 °C, while {100}-bound nanocubes start to sinter above 250 °C. The highest benzene yield has been observed on gold-iron oxide nanooctahedra, which are likely to have gold atoms, and few-atom gold clusters strongly-bound on their surface. Cationic gold appears to be the active site for benzene formation. An all-organic method to prepare Au-FeOx nano-catalysts is needed due to the inconvenience of the half-organic, half-inorganic synthesis process discussed above. Several methods from the literature to prepare gold-iron oxide nanocomposites completely in organic solvents were reviewed and followed. FeOx Au synthesis procedures in literatures are initially designed for a Au content of over 70%. This approach was tried here to prepare composites with a much lower Au content (2-5 atom. %). Heat treatment is required to bond Au and FeOx NPs in the organic-phase syntheses. Au-FeOx-4 was obtained as a selective catalyst for the ODH of cyclohexane. A Audelta+ peak is observed in the UV-Vis spectrum of sample Au-FeOx-4. This different Au delta+ form may be cationic Au nano-clusters interacting with the FeOx support. It has been demonstrated that cationic gold is responsible for dehydrogenation behavior. Furthermore, the

  14. Size selected metal clusters

    Indian Academy of Sciences (India)

    First page Back Continue Last page Overview Graphics. The Optical Absorption Spectra of Small Silver Clusters (5-11) ... Soft Landing and Fragmentation of Small Clusters Deposited in Noble-Gas Films. Harbich, W.; Fedrigo, S.; Buttet, J. Phys. Rev. B 1998, 58, 7428. CO combustion on supported gold clusters. Arenz M ...

  15. Cluster-cluster clustering

    International Nuclear Information System (INIS)

    Barnes, J.; Dekel, A.; Efstathiou, G.; Frenk, C.S.; Yale Univ., New Haven, CT; California Univ., Santa Barbara; Cambridge Univ., England; Sussex Univ., Brighton, England)

    1985-01-01

    The cluster correlation function xi sub c(r) is compared with the particle correlation function, xi(r) in cosmological N-body simulations with a wide range of initial conditions. The experiments include scale-free initial conditions, pancake models with a coherence length in the initial density field, and hybrid models. Three N-body techniques and two cluster-finding algorithms are used. In scale-free models with white noise initial conditions, xi sub c and xi are essentially identical. In scale-free models with more power on large scales, it is found that the amplitude of xi sub c increases with cluster richness; in this case the clusters give a biased estimate of the particle correlations. In the pancake and hybrid models (with n = 0 or 1), xi sub c is steeper than xi, but the cluster correlation length exceeds that of the points by less than a factor of 2, independent of cluster richness. Thus the high amplitude of xi sub c found in studies of rich clusters of galaxies is inconsistent with white noise and pancake models and may indicate a primordial fluctuation spectrum with substantial power on large scales. 30 references

  16. Cluster dynamics at different cluster size and incident laser wavelengths

    International Nuclear Information System (INIS)

    Desai, Tara; Bernardinello, Andrea

    2002-01-01

    X-ray emission spectra from aluminum clusters of diameter -0.4 μm and gold clusters of dia. ∼1.25 μm are experimentally studied by irradiating the cluster foil targets with 1.06 μm laser, 10 ns (FWHM) at an intensity ∼10 12 W/cm 2 . Aluminum clusters show a different spectra compared to bulk material whereas gold cluster evolve towards bulk gold. Experimental data are analyzed on the basis of cluster dimension, laser wavelength and pulse duration. PIC simulations are performed to study the behavior of clusters at higher intensity I≥10 17 W/cm 2 for different size of the clusters irradiated at different laser wavelengths. Results indicate the dependence of cluster dynamics on cluster size and incident laser wavelength

  17. Investigating the synthesis of ligated metal clusters in solution using a flow reactor and electrospray ionization mass spectrometry.

    Science.gov (United States)

    Olivares, Astrid; Laskin, Julia; Johnson, Grant E

    2014-09-18

    The scalable synthesis of ligated subnanometer metal clusters containing an exact number of atoms is of interest due to the highly size-dependent catalytic, electronic, and optical properties of these species. While significant research has been conducted on the batch preparation of clusters through reduction synthesis in solution, the processes of metal complex reduction as well as cluster nucleation, growth, and postreduction etching are still not well understood. Herein, we demonstrate a prototype temperature-controlled flow reactor for qualitatively studying cluster formation in solution at steady-state conditions. Employing this technique, methanol solutions of a chloro(triphenylphosphine)gold precursor, 1,4-bis(diphenylphosphino)butane capping ligand, and borane-tert-butylamine reducing agent were combined in a mixing tee and introduced into a heated capillary with a known length. In this manner, the temperature dependence of the relative abundance of different ionic reactants, intermediates, and products synthesized in real time was characterized qualitatively using online mass spectrometry. A wide distribution of doubly and triply charged cationic gold clusters was observed as well as smaller singly charged organometallic complexes. The results demonstrate that temperature plays a crucial role in determining the relative population of cationic gold clusters and, in general, that higher temperature promotes the formation of doubly charged clusters and singly charged organometallic complexes while reducing the abundance of triply charged species. Moreover, the distribution of clusters observed at elevated temperatures is found to be consistent with that obtained at longer reaction times at room temperature, thereby demonstrating that heating may be used to access cluster distributions characteristic of different stages of batch reduction synthesis in solution.

  18. Gold prices

    OpenAIRE

    Joseph G. Haubrich

    1998-01-01

    The price of gold commands attention because it serves as an indicator of general price stability or inflation. But gold is also a commodity, used in jewelry and by industry, so demand and supply affect its pricing and need to be considered when gold is a factor in monetary policy decisions.

  19. Subnanometer Gold Clusters on Amino-Functionalized Silica: An Efficient Catalyst for the Synthesis of 1,3-Diynes by Oxidative Alkyne Coupling

    Czech Academy of Sciences Publication Activity Database

    Vilhanová, B.; Václavík, Jiří; Artiglia, L.; Ranocchiari, M.; Togni, A.; van Bokhoven, J. A.

    2017-01-01

    Roč. 7, č. 5 (2017), s. 3414-3418 ISSN 2155-5435 Institutional support: RVO:61388963 Keywords : alkyne coupling * gold * heterogeneous catalysis * hypervalent iodine * subnanometer Subject RIV: CC - Organic Chemistry OBOR OECD: Organic chemistry Impact factor: 10.614, year: 2016

  20. Vacancy clusters at nanoparticle surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Xu, J.; Moxom, J.; Somieski, B.; White, C.W. [Oak Ridge National Lab., TN (United States); Mills, A.P. Jr. [Bell Labs., Lucent Technologies, Murray Hill, NJ (United States); Suzuki, R.; Ishibashi, S. [Electrotechnical Lab., Tsukuba, Ibaraki (Japan); Ueda, A.; Henderson, D. [Physics Dept., Fisk Univ., Nashville, TN (United States)

    2001-07-01

    We detect vacancy clusters at Au nanoparticle surfaces using a combination of positron lifetime spectroscopy, 1- detector, and 2-detector measurements of Doppler broadening of annihilation radiation. Gold nanoparticles are formed by MeV implantation of gold ions into MgO (100) followed by annealing. Clusters of two Mg and two O vacancies (v{sub 4}) are attached to the gold nanoparticle surfaces within the projected range (R{sub p}). (orig.)

  1. Vacancy clusters at nanoparticle surfaces

    International Nuclear Information System (INIS)

    Xu, J.; Moxom, J.; Somieski, B.; White, C.W.; Mills, A.P. Jr.; Suzuki, R.; Ishibashi, S.; Ueda, A.; Henderson, D.

    2001-01-01

    We detect vacancy clusters at Au nanoparticle surfaces using a combination of positron lifetime spectroscopy, 1- detector, and 2-detector measurements of Doppler broadening of annihilation radiation. Gold nanoparticles are formed by MeV implantation of gold ions into MgO (100) followed by annealing. Clusters of two Mg and two O vacancies (v 4 ) are attached to the gold nanoparticle surfaces within the projected range (R p ). (orig.)

  2. Implications of Pearl, Gold, Silver (PGS) craft industrial cluster towards settlements region in Karang Pule Village, Sekarbela District Of Mataram City

    Science.gov (United States)

    Sushanti, I. R.; Fitri, I. S.

    2017-06-01

    The existence of industry clusters in Mataram City gave effect to the surrounding residential areas [1]. In accordance Spatial Plan of Mataram City in 2011-2031 PGS industry cluster in the village of Karang Pule, Sekarbela district established as shopping tourism area. Distribution of industrial locations were in four of seven environments in Karang Pule. Distribution of PGS industry is divided into three (3) groups: craftsmen, craftsmen who is also a seller, and the seller (merchant). The location of the craftsmen, craftsmen who are also businessmen and entrepreneurs are also used as a dwelling house or workshop and store. So most of the people living in settlements around clusters of industry that there is a link between industry cluster and settlements. This study aims to determine the implications or the impact of the presence of PGS industry clusters the surrounding residential areas. The method used in this research is descriptive qualitative with the collection of primary data through direct observation and questionnaires. Based on direct observation on the shopping tourism area there are inequality between the conditions of industry clusters and settlements area by the presence of slums. The results showed that the PGS industry cluster impact on social, economic and environment near settlements area. Impacts that occur are: 1) the social aspect, there is a significant change in the level of education, social welfare and social disparities but less significant to the formation of institutions, particularly in community participation, 2) the economic aspect of the change status of community work, and increased revenue and 3) the environmental aspects of the change to the condition of the building, the quality of public housing, the presence of slums, changes in infrastructure and the environmental pollution.

  3. Isomerization of propargyl cation to cyclopropenyl cation ...

    Indian Academy of Sciences (India)

    step) for isomeri- zation of the linear propargyl cation to ..... C3, C4 and C5. The ZPE corrections in each case are derived from the. B3LYP calculations. ..... the converse of which gives the relative capacity of the. LPD's to stabilize TS6 with respect ...

  4. Gold Returns

    OpenAIRE

    Robert J. Barro; Sanjay P. Misra

    2013-01-01

    From 1836 to 2011, the average real rate of price change for gold in the United States is 1.1% per year and the standard deviation is 13.1%, implying a one-standard-deviation confidence band for the mean of (0.1%, 2.1%). The covariances of gold's real rate of price change with consumption and GDP growth rates are small and statistically insignificantly different from zero. These negligible covariances suggest that gold's expected real rate of return--which includes an unobserved dividend yiel...

  5. Nonlinear optical studies of single gold nanoparticles

    NARCIS (Netherlands)

    Dijk, Meindert Alexander van

    2007-01-01

    Gold nanoparticles are spherical clusters of gold atoms, with diameters typically between 1 and 100 nanometers. The applications of these particles are rather diverse, from optical labels for biological experiments to data carrier for optical data storage. The goal of my project was to develop new

  6. Studying the varied shapes of gold clusters by an elegant optimization algorithm that hybridizes the density functional tight-binding theory and the density functional theory

    Science.gov (United States)

    Yen, Tsung-Wen; Lim, Thong-Leng; Yoon, Tiem-Leong; Lai, S. K.

    2017-11-01

    We combined a new parametrized density functional tight-binding (DFTB) theory (Fihey et al. 2015) with an unbiased modified basin hopping (MBH) optimization algorithm (Yen and Lai 2015) and applied it to calculate the lowest energy structures of Au clusters. From the calculated topologies and their conformational changes, we find that this DFTB/MBH method is a necessary procedure for a systematic study of the structural development of Au clusters but is somewhat insufficient for a quantitative study. As a result, we propose an extended hybridized algorithm. This improved algorithm proceeds in two steps. In the first step, the DFTB theory is employed to calculate the total energy of the cluster and this step (through running DFTB/MBH optimization for given Monte-Carlo steps) is meant to efficiently bring the Au cluster near to the region of the lowest energy minimum since the cluster as a whole has explicitly considered the interactions of valence electrons with ions, albeit semi-quantitatively. Then, in the second succeeding step, the energy-minimum searching process will continue with a skilledly replacement of the energy function calculated by the DFTB theory in the first step by one calculated in the full density functional theory (DFT). In these subsequent calculations, we couple the DFT energy also with the MBH strategy and proceed with the DFT/MBH optimization until the lowest energy value is found. We checked that this extended hybridized algorithm successfully predicts the twisted pyramidal structure for the Au40 cluster and correctly confirms also the linear shape of C8 which our previous DFTB/MBH method failed to do so. Perhaps more remarkable is the topological growth of Aun: it changes from a planar (n =3-11) → an oblate-like cage (n =12-15) → a hollow-shape cage (n =16-18) and finally a pyramidal-like cage (n =19, 20). These varied forms of the cluster's shapes are consistent with those reported in the literature.

  7. Formation of neutral and charged gold carbonyls on highly facetted gold nanostructures

    Science.gov (United States)

    Chau, Thoi-Dai; Visart de Bocarmé, Thierry; Kruse, Norbert; Wang, Richard L. C.; Kreuzer, Hans Jürgen

    2003-12-01

    We show that gold mono- and di-carbonyls are formed on gold field emitter tips during interaction with carbon monoxide gas at room temperature and in the presence of high electrostatic fields. The experiments are done in a time-of-flight atom probe to obtain mass spectra. The yield of monocarbonyl cations is about twice that of di-carbonyl ions. Density functional theory calculations are reported that explain the field stabilization of adsorbed carbonyls and the desorption yield of their cations.

  8. Gold monetization and gold discipline

    OpenAIRE

    Robert P. Flood; Peter M. Garber

    1981-01-01

    The paper is a study of the price level and relative price effects of a policy to monetize gold and fix its price at a given future time and at the then prevailing nominal price. Price movements are analyzed both during the transition to the gold standard and during the post-monetization period. The paper also explores the adjustments to fiat money which are necessary to ensure that this type of gold monetization is non-inflationary. Finally, some conditions which produce a run on the governm...

  9. Cation Exchange Water Softeners

    Science.gov (United States)

    WaterSense released a notice of intent to develop a specification for cation exchange water softeners. The program has made the decision not to move forward with a spec at this time, but is making this information available.

  10. CO oxidation on gold nanoparticles: Theoretical studies

    DEFF Research Database (Denmark)

    Remediakis, Ioannis; Lopez, Nuria; Nørskov, Jens Kehlet

    2005-01-01

    We present a summary of our theoretical results regarding CO oxidation on both oxide-supported and isolated gold nanoparticles. Using Density Functional Theory we have studied the adsorption of molecules and the oxidation reaction of CO on gold clusters. Low-coordinated sites on the gold...... nanoparticles can adsorb small inorganic molecules such as O2 and CO, and the presence of these sites is the key factor for the catalytic properties of supported gold nanoclusters. Other contributions, induced by the presence of the support, can provide parallel channels for the reaction and modulate the final...

  11. Enhanced thermal lens effect in gold nanoparticle-doped Lyotropic liquid crystal by nanoparticle clustering probed by Z-scan technique

    International Nuclear Information System (INIS)

    Gomez, S.L.; Lenart, V.M.

    2015-01-01

    This work presents an experimental study of the thermal lens effect in Au nanoparticles-doped lyotropic liquid crystals under cw 532 nm optical excitation. Spherical Au nanoparticles of about 12 nm were prepared by Turkevich’s method, and the lyotropic liquid crystal was a ternary mixture of SDS, 1-DeOH, and water that exhibits an isotropic phase at room temperature. The lyotropic matrix induces aggregation of the nanoparticles, leading to a broad and a red-shifted surface plasmon resonance. The thermal nonlinear optical refraction coefficient n 2 increases as a power of number density of nanoparticles, being possible to address this behavior to nanoparticle clustering. (author)

  12. Enhanced thermal lens effect in gold nanoparticle-doped Lyotropic liquid crystal by nanoparticle clustering probed by Z-scan technique

    Energy Technology Data Exchange (ETDEWEB)

    Gomez, S.L.; Lenart, V.M., E-mail: sgomez@uepg.br [Universidade Estadual de Ponta Grossa (UEPG), PR (Brazil). Dept. de Fisica; Turchiello, R.T. [Universidade Federal Tecnologica do Parana (UFTPR), Ponta Grossa, PR (Brazil). Dept. de Fisica; Goya, G.F. [Department of Condensed Matter Physics, Aragon Institute of Nanoscience, Zaragoza (Spain)

    2015-10-01

    This work presents an experimental study of the thermal lens effect in Au nanoparticles-doped lyotropic liquid crystals under cw 532 nm optical excitation. Spherical Au nanoparticles of about 12 nm were prepared by Turkevich’s method, and the lyotropic liquid crystal was a ternary mixture of SDS, 1-DeOH, and water that exhibits an isotropic phase at room temperature. The lyotropic matrix induces aggregation of the nanoparticles, leading to a broad and a red-shifted surface plasmon resonance. The thermal nonlinear optical refraction coefficient n{sub 2} increases as a power of number density of nanoparticles, being possible to address this behavior to nanoparticle clustering. (author)

  13. Structure and Stability of GeAun, n = 1-10 clusters: A Density Functional Study

    International Nuclear Information System (INIS)

    Priyanka,; Dharamvir, Keya; Sharma, Hitesh

    2011-01-01

    The structures of Germanium doped gold clusters GeAu n (n = 1-10) have been investigated using ab initio calculations based on density functional theory (DFT). We have obtained ground state geometries of GeAu n clusters and have it compared with Silicon doped gold clusters and pure gold clusters. The ground state geometries of the GeAu n clusters show patterns similar to silicon doped gold clusters except for n = 5, 6 and 9. The introduction of germanium atom increases the binding energy of gold clusters. The binding energy per atom of germanium doped cluster is smaller than the corresponding silicon doped gold cluster. The HUMO-LOMO gap for Au n Ge clusters have been found to vary between 0.46 eV-2.09 eV. The mullikan charge analysis indicates that charge of order of 0.1e always transfers from germanium atom to gold atom.

  14. Gold Museum

    OpenAIRE

    Efraín Sánchez Cabra

    2003-01-01

    On 22 december 1939, the Banco de la República, the Central Bank of Colombia, purchased a 23.5 centimetres high pre-Columbian gold arte fact weighing 777·7 grams that was to become the Gold M useum's foundation stone. Described as a Quimbaya poporo, it is a masterpiece of pre-Hispanic goldwork, an object of beauty whose brightly burnished body and neck, crowned with four sphere-like or naments, rest on an exquisite cast metal tiligree base and which seems to ftoat in a space of its own. The b...

  15. Goldenphilicity: Luminescent gold compounds

    International Nuclear Information System (INIS)

    Sansores, L.E.

    2002-01-01

    In the solids and molecules different types of bonds are presented depending on the involved atoms, covalent bonds are common among elements of open shell, where more bond orbitals are filled than anti bond orbitals. It is expected that ionic bonds among closed shell atoms which have charges of opposite sign. Bonds type Van der Waals are presented among molecules which have a bipolar moment. It would not be expected bonds among zero charge species, or more generally with the same nominal charge and in any case the attractive forces would be very small. In fact it is expected that two metallic cations to be repelled each other. There recently is evidence that in organic or organometallic compounds could exist attractive interactions between two cations of the d 8 -d 10 -s 2 families. These bonds are weak but stronger than those of Van der Waals. They are compared with the hydrogen bonds. In this work it was reviewed some examples in which the goldenphilicity plays an important role in the luminescence that the gold complexes present. Examples of mono, bi and trinuclear and the structures that these organometallic compounds could take are examined. (Author)

  16. Green Gold

    International Nuclear Information System (INIS)

    Salamandra Martinez, Carlos

    2004-01-01

    The main purpose of this work is to offer a general panoramic of the processes or experiences pilot that are carried out in the Project Green Gold, as strategy of environmental sustainability and organizational invigoration in Choco, especially in the 12 communities of the municipalities of Tado and Condoto. It is also sought to offer a minimum of information on the techniques of handmade production and to show the possibilities to carry out in a rational way the use and use of the natural resources. The Project Green Gold is carried out by the Corporation Green Gold (COV) and co-financed with resources of international and national character, the intervention of the financial resources it achievement mainly for the use of clean processes in the extraction stages and metals benefit. The project is centered primarily in the absence of use of products or toxic substances as the mercury, fair trade, organizational invigoration, execution of 11 approaches and certification of the metals Gold and Platinum. The COV, it has come executing the proposal from the year 2001 with the premise of contributing to the balance between the rational exploitation of the natural resources and the conservation of the environment in the Choco. In the project they are used technical handmade characteristic of the region framed inside the mining activity and production activities are diversified in the productive family units. Those producing with the support of entities of juridical character, specify the necessary game rules for the extraction and products commercialization

  17. Cation radicals of xanthophylls.

    Science.gov (United States)

    Galinato, Mary Grace I; Niedzwiedzki, Dariusz; Deal, Cailin; Birge, Robert R; Frank, Harry A

    2007-10-01

    Carotenes and xanthophylls are well known to act as electron donors in redox processes. This ability is thought to be associated with the inhibition of oxidative reactions in reaction centers and light-harvesting pigment-protein complexes of photosystem II (PSII). In this work, cation radicals of neoxanthin, violaxanthin, lutein, zeaxanthin, beta-cryptoxanthin, beta-carotene, and lycopene were generated in solution using ferric chloride as an oxidant and then studied by absorption spectroscopy. The investigation provides a view toward understanding the molecular features that determine the spectral properties of cation radicals of carotenoids. The absorption spectral data reveal a shift to longer wavelength with increasing pi-chain length. However, zeaxanthin and beta-cryptoxanthin exhibit cation radical spectra blue-shifted compared to that of beta-carotene, despite all of these molecules having 11 conjugated carbon-carbon double bonds. CIS molecular orbital theory quantum computations interpret this effect as due to the hydroxyl groups in the terminal rings selectively stabilizing the highest occupied molecular orbitals of preferentially populated s-trans-isomers. The data are expected to be useful in the analysis of spectral results from PSII pigment-protein complexes seeking to understand the role of carotene and xanthophyll cation radicals in regulating excited state energy flow, in protecting PSII reaction centers against photoinhibition, and in dissipating excess light energy absorbed by photosynthetic organisms but not used for photosynthesis.

  18. Identifi cation of Sectarianism

    Directory of Open Access Journals (Sweden)

    Martinovich Vladimir

    2016-03-01

    Full Text Available «New religious movements and society» is traditionally one of the most sophisticated topics in the area of new religions studies. Its problem field is so huge that up to now by far not all important research themes where even touched by scientists from all over the world. The problem of the process of the identification of sectarianism by diff erent societal institutions is one of such untouched themes that is taken as the main subject of this article. This process by itself is an inseparable part of the every societal deliberate reaction to the very existence of unconventional religiosity, its unstructured and mainly structured types. The focal point of the article is step-by-step analysis of the general structure elements of the process of the identification of sectarianism without any reference to the specific time and place of its flow. Special attention is paid to the analysis of the subjects of the identification of sectarianism, to the criteria for religious groups to be qualified as new religious movements, and to the specific features of the process of documents filtration. The causes of selective perception of sectarianism are disclosed. Some main consequences and unpredictable outcomes of the process of the identification of sectarianism are described.

  19. Comprehensive cluster analysis with Transitivity Clustering.

    Science.gov (United States)

    Wittkop, Tobias; Emig, Dorothea; Truss, Anke; Albrecht, Mario; Böcker, Sebastian; Baumbach, Jan

    2011-03-01

    Transitivity Clustering is a method for the partitioning of biological data into groups of similar objects, such as genes, for instance. It provides integrated access to various functions addressing each step of a typical cluster analysis. To facilitate this, Transitivity Clustering is accessible online and offers three user-friendly interfaces: a powerful stand-alone version, a web interface, and a collection of Cytoscape plug-ins. In this paper, we describe three major workflows: (i) protein (super)family detection with Cytoscape, (ii) protein homology detection with incomplete gold standards and (iii) clustering of gene expression data. This protocol guides the user through the most important features of Transitivity Clustering and takes ∼1 h to complete.

  20. Determination of gold in gold ores

    International Nuclear Information System (INIS)

    Keedy, C.R.; Parson, L.; Shen, J.

    1989-01-01

    The gold content of placer gold flakes and gold bearing ores was determined by instrumental and radiochemical neutron activation analysis, respectively. It was discovered that significant errors result in the instrumental method for gold flakes as small as 10 mg due to sample self-absorption of neutrons during irradiation. Reliable results were obtained for both ore samples and gold flakes by dissolving the samples in aqua regia prior to irradiation. (author) 7 refs.; 3 tabs

  1. Silver and gold in the Protein Data Bank.

    Science.gov (United States)

    Carugo, Oliviero

    2017-10-01

    The structural features of the silver and gold sites in protein crystal structures extracted from the Protein Data Bank have been investigated. It is observed that both cations have nearly always low oxidations states (+1) and low coordination numbers, adopt standard stereochemistries, and interact preferentially (particularly gold) with sulfur donor atoms of cysteine and methionine side-chains. Interestingly, gold cation have been very often refined with occupancy minor than 1.0 and are very often "naked", in the sense that no donor atoms are sufficiently close to the metal cation. This apparently strange observation points out towards the need to develop specific and efficient validation tools for these elements when they are coordinated to proteins. Copyright © 2017 Elsevier Inc. All rights reserved.

  2. New Trends in Gold Catalysts

    Directory of Open Access Journals (Sweden)

    Leonarda F. Liotta

    2014-07-01

    Full Text Available Gold is an element that has fascinated mankind for millennia. The catalytic properties of gold have been a source of debate, due to its complete chemical inertness when in a bulk form, while it can oxidize CO at temperatures as low as ~200 K when in a nanocrystalline state, as discovered by Haruta in the late 1980s [1]. Since then, extensive activity in both applied and fundamental research on gold has been initiated. The importance of the catalysis by gold represents one of the fasted growing fields in science and is proven by the promising applications in several fields, such as green chemistry and environmental catalysis, in the synthesis of single-walled carbon nanotubes, as modifiers of Ni catalysts for methane steam and dry reforming reactions and in biological and electrochemistry applications. The range of reactions catalyzed by gold, as well as the suitability of different supports and the influence of the preparation conditions have been widely explored and optimized in applied research [2]. Gold catalysts appeared to be very different from the other noble metal-based catalysts, due to their marked dependence on the preparation method, which is crucial for the genesis of the catalytic activity. Several methods, including deposition-precipitation, chemical vapor deposition and cation adsorption, have been applied for the preparation of gold catalysts over reducible oxides, like TiO2. Among these methods, deposition-precipitation has been the most frequently employed method for Au loading, and it involves the use of tetrachloroauric (III acid as a precursor. On the other hand, the number of articles dealing with Au-loaded acidic supports is smaller than that on basic supports, possibly because the deposition of [AuCl4]− or [AuOHxCl4−x]− species on acidic supports is difficult, due to their very low point of zero charge. Despite this challenge, several groups have reported the use of acidic zeolites as supports for gold. Zeolites

  3. Cation Binding to Xanthorhodopsin: Electron Paramagnetic Resonance and Magnetic Studies.

    Science.gov (United States)

    Smolensky Koganov, Elena; Leitus, Gregory; Rozin, Rinat; Weiner, Lev; Friedman, Noga; Sheves, Mordechai

    2017-05-04

    Xanthorhodopsin (xR) is a member of the retinal protein family and acts as a proton pump in the cell membranes of the extremely halophilic eubacterium Salinibacter ruber. In addition to the retinal chromophore, xR contains a carotenoid, which acts as a light-harvesting antenna as it transfers 40% of the quanta it absorbs to the retinal. Our previous studies have shown that the CD and absorption spectra of xR are dramatically affected due to the protonation of two different residues. It is still unclear whether xR can bind cations. Electron paramagnetic resonance (EPR) spectroscopy used in the present study revealed that xR can bind divalent cations, such as Mn 2+ and Ca 2+ , to deionized xR (DI-xR). We also demonstrate that xR can bind 1 equiv of Mn 2+ to a high-affinity binding site followed by binding of ∼40 equiv in cooperative manner and ∼100 equiv of Mn 2+ that are weakly bound. SQUID magnetic studies suggest that the high cooperative binding of Mn 2+ cations to xR is due to the formation of Mn 2+ clusters. Our data demonstrate that Ca 2+ cations bind to DI-xR with a lower affinity than Mn 2+ , supporting the assumption that binding of Mn 2+ occurs through cluster formation, because Ca 2+ cations cannot form clusters in contrast to Mn 2+ .

  4. Clustering of near clusters versus cluster compactness

    International Nuclear Information System (INIS)

    Yu Gao; Yipeng Jing

    1989-01-01

    The clustering properties of near Zwicky clusters are studied by using the two-point angular correlation function. The angular correlation functions for compact and medium compact clusters, for open clusters, and for all near Zwicky clusters are estimated. The results show much stronger clustering for compact and medium compact clusters than for open clusters, and that open clusters have nearly the same clustering strength as galaxies. A detailed study of the compactness-dependence of correlation function strength is worth investigating. (author)

  5. Oxidation state of gold and arsenic in gold-bearing arsenian pyrite

    Energy Technology Data Exchange (ETDEWEB)

    Simon, G.; Huang, H.; Penner-Hahn, J.E.; Kesler, S.E.; Kao, L.S. [Univ. of Michigan, Ann Arbor, MI (United States)

    1999-07-01

    XANES measurements on gold-bearing arsenian pyrite from the Twin Creeks Carlin-type gold deposits show that gold is present as both Au{sup 0} and Au{sup 1+} and arsenic is present as As{sup 1{minus}}. Au{sup 0} is attributed to sub-micrometer size inclusions of free gold, whereas Au{sup 1+} is attributed to gold in the lattice of the arsenian pyrite. STEM observations suggest that As{sup 1{minus}} is probably concentrated in angstrom-scale, randomly distributed layers with a marcasite or arsenopyrite structure. Ionic gold (Au{sup 1+}) could be concentrated in these layers as well, and is present in both twofold- and fourfold-coordinated forms, with fourfold-coordinated Au{sup 1+} more abundant. Twofold-coordinated Au{sup 1+} is similar to gold in Au{sub 2}S in which it is linearly coordinated to two sulfur atoms. The nature of fourfold-coordinated Au{sup 1+} is not well understood, although it might be present as an Au-As-S compound where gold is bonded in fourfold coordination to sulfur and arsenic atoms, or in vacancy positions on a cation site in the arsenian pyrite. Au{sup 1+} was probably incorporated into arsenian pyrite by adsorption onto pyrite surfaces during crystal growth. The most likely compound in the case of twofold-coordinated Au{sup 1+} was probably a tri-atomic surface complex such as S{sub pyrite}-Au{sup 1+}-S{sub bi-sulfide}H or Au{sup 1+}-S-Au{sup 1+}. The correlation between gold and arsenic might be related to the role of arsenic in enhancing the adsorption of gold complexes of this type on pyrite surfaces, possibly through semiconductor effects.

  6. Sorption by cation exchange

    International Nuclear Information System (INIS)

    Bradbury, M.H.; Baeyens, B.

    1994-04-01

    A procedure for introducing exchange into geochemical/surface complexation codes is described. Beginning with selectivity coefficients, K c , defined in terms of equivalent fractional ion occupancies, a general expression for the molar based exchange code input parameters, K ex , is derived. In natural systems the uptake of nuclides onto complex sorbents often occurs by more than one mechanism. The incorporation of cation exchange and surface complexation into a geochemical code therefore enables sorption by both mechanisms to be calculated simultaneously. The code and model concepts are tested against sets of experimental data from widely different sorption studies. A proposal is made to set up a data base of selectivity coefficients. Such a data base would form part of a more general one consisting of sorption mechanism specific parameters to be used in conjunction with geochemical/sorption codes to model and predict sorption. (author) 6 figs., 6 tabs., 26 refs

  7. Computer simulation of the vertical growth of subsurface cobalt nanoclusters in gold

    NARCIS (Netherlands)

    Kulikov, D.V.; Kurnosikov, O.; Sicot, M.V.; Trushin, Yu.V.

    2009-01-01

    The vertical growth of nanodimensional cobalt clusters buried under the surface of a gold substrate has been studied using computer simulation methods with allowance for the interdiffusion of Au and Co atoms and the fields of elastic stresses generated by cobalt clusters in the gold matrix. The

  8. Gas phase reactivity of thermal metal clusters

    International Nuclear Information System (INIS)

    Castleman, A.W. Jr.; Harms, A.C.; Leuchtner, R.E.

    1991-01-01

    Reaction kinetics of metal cluster ions under well defined thermal conditions were studied using a flow tube reactor in combination with laser vaporization. Aluminum anions and cations were reacted with oxygen, and several species which are predicted jellium shell closings, were found to have special stability. Metal alloy cluster anions comprised of Al, V and Nb were also seen to react with oxygen. Alloy clusters with an even number of electrons reacted more slowly than odd electron species, and certain clusters appeared to be exceptionally unreactive. Copper cation clusters were observed to associate with carbon monoxide with reactivities that approach bulk behavior at surprisingly small cluster size. These reactions demonstrate how the rate of reaction changes with cluster size. (orig.)

  9. Gas phase reactivity of thermal metal clusters

    Science.gov (United States)

    Castleman, A. W., Jr.; Harms, A. C.; Leuchtner, R. E.

    1991-03-01

    Reaction kinetics of metal cluster ions under well defined thermal conditions were studied using a flow tube reactor in combination with laser vaporization. Aluminum anions and cations were reacted with oxygen, and several species which are predicted jellium shell closings, were found to have special stability. Metal alloy cluster anions comprised of Al, V and Nb were also seen to react with oxygen. Alloy clusters with an even number of electrons reacted more slowly than odd electron species, and certain clusters appeared to be exceptionally unreactive. Copper cation clusters were observed to associate with carbon monoxide with reactivities that approach bulk behavior at surprisingly small cluster size. These reactions demonstrate how the rate of reaction changes with cluster size.

  10. Plasmon resonances in large noble-metal clusters

    International Nuclear Information System (INIS)

    Soennichsen, C; Franzl, T; Wilk, T; Plessen, G von; Feldmann, J

    2002-01-01

    We investigate the optical properties of spherical gold and silver clusters with diameters of 20 nm and larger. The light scattering spectra of individual clusters are measured using dark-field microscopy, thus avoiding inhomogeneous broadening effects. The dipolar plasmon resonances of the clusters are found to have nearly Lorentzian line shapes. With increasing size we observe polaritonic red-shifts of the plasmon line and increased radiation damping for both gold and silver clusters. Apart from some cluster-to-cluster variations of the plasmon lines, agreement with Mie theory is reasonably good for the gold clusters. However, it is less satisfactory for the silver clusters, possibly due to cluster faceting or chemical effects

  11. Synthesis of gold nanoclusters: a fluorescent marker for water-soluble TiO2 nanotubes

    International Nuclear Information System (INIS)

    Ratanatawanate, Chalita; Yu Jing; Zhou Chen; Zheng Jie; Balkus, Kenneth J Jr

    2011-01-01

    The first example of a water-soluble wrapped titania nanotube (TNT) decorated with fluorescent gold nanoparticles has been prepared. Gold nanoparticles ∼ 1.6 nm in diameter were grown on the TiO 2 nanotubes using a thiolactic acid linker to control the size. The gold clusters emit at 660 nm in water and were imaged using confocal microscopy. The gold decorated TNTs were suspended in water by wrapping the nanotubes with poly-L-arginine.

  12. Cationic polymers and porous materials

    KAUST Repository

    Han, Yu

    2017-04-27

    According to one or more embodiments, cationic polymers may be produced which include one or more monomers containing cations. Such cationic polymers may be utilized as structure directing agents to form mesoporous zeolites. The mesoporous zeolites may include micropores as well as mesopores, and may have a surface area of greater than 350 m2/g and a pore volume of greater than 0.3 cm3/g. Also described are core/shell zeolites, where at least the shell portion includes a mesoporous zeolite material.

  13. Cationic polymers and porous materials

    KAUST Repository

    Han, Yu; Tian, Qiwei; Dong, Xinglong; Liu, Zhaohui; Basset, Jean-Marie; Saih, Youssef; Sun, Miao; Xu, Wei; Shaikh, Sohel

    2017-01-01

    According to one or more embodiments, cationic polymers may be produced which include one or more monomers containing cations. Such cationic polymers may be utilized as structure directing agents to form mesoporous zeolites. The mesoporous zeolites may include micropores as well as mesopores, and may have a surface area of greater than 350 m2/g and a pore volume of greater than 0.3 cm3/g. Also described are core/shell zeolites, where at least the shell portion includes a mesoporous zeolite material.

  14. The cation-π interaction.

    Science.gov (United States)

    Dougherty, Dennis A

    2013-04-16

    The chemistry community now recognizes the cation-π interaction as a major force for molecular recognition, joining the hydrophobic effect, the hydrogen bond, and the ion pair in determining macromolecular structure and drug-receptor interactions. This Account provides the author's perspective on the intellectual origins and fundamental nature of the cation-π interaction. Early studies on cyclophanes established that water-soluble, cationic molecules would forego aqueous solvation to enter a hydrophobic cavity if that cavity was lined with π systems. Important gas phase studies established the fundamental nature of the cation-π interaction. The strength of the cation-π interaction (Li(+) binds to benzene with 38 kcal/mol of binding energy; NH4(+) with 19 kcal/mol) distinguishes it from the weaker polar-π interactions observed in the benzene dimer or water-benzene complexes. In addition to the substantial intrinsic strength of the cation-π interaction in gas phase studies, the cation-π interaction remains energetically significant in aqueous media and under biological conditions. Many studies have shown that cation-π interactions can enhance binding energies by 2-5 kcal/mol, making them competitive with hydrogen bonds and ion pairs in drug-receptor and protein-protein interactions. As with other noncovalent interactions involving aromatic systems, the cation-π interaction includes a substantial electrostatic component. The six (four) C(δ-)-H(δ+) bond dipoles of a molecule like benzene (ethylene) combine to produce a region of negative electrostatic potential on the face of the π system. Simple electrostatics facilitate a natural attraction of cations to the surface. The trend for (gas phase) binding energies is Li(+) > Na(+) > K(+) > Rb(+): as the ion gets larger the charge is dispersed over a larger sphere and binding interactions weaken, a classical electrostatic effect. On other hand, polarizability does not define these interactions. Cyclohexane is

  15. Synthetic cation-selective nanotube: permeant cations chaperoned by anions.

    Science.gov (United States)

    Hilder, Tamsyn A; Gordon, Dan; Chung, Shin-Ho

    2011-01-28

    The ability to design ion-selective, synthetic nanotubes which mimic biological ion channels may have significant implications for the future treatment of bacteria, diseases, and as ultrasensitive biosensors. We present the design of a synthetic nanotube made from carbon atoms that selectively allows monovalent cations to move across and rejects all anions. The cation-selective nanotube mimics some of the salient properties of biological ion channels. Before practical nanodevices are successfully fabricated it is vital that proof-of-concept computational studies are performed. With this in mind we use molecular and stochastic dynamics simulations to characterize the dynamics of ion permeation across a single-walled (10, 10), 36 Å long, carbon nanotube terminated with carboxylic acid with an effective radius of 5.08 Å. Although cations encounter a high energy barrier of 7 kT, its height is drastically reduced by a chloride ion in the nanotube. The presence of a chloride ion near the pore entrance thus enables a cation to enter the pore and, once in the pore, it is chaperoned by the resident counterion across the narrow pore. The moment the chaperoned cation transits the pore, the counterion moves back to the entrance to ferry another ion. The synthetic nanotube has a high sodium conductance of 124 pS and shows linear current-voltage and current-concentration profiles. The cation-anion selectivity ratio ranges from 8 to 25, depending on the ionic concentrations in the reservoirs.

  16. Correlation between the Increasing Conductivity of Aqueous Solutions of Cation Chlorides with Time and the “Salting-Out” Properties of the Cations

    Directory of Open Access Journals (Sweden)

    Nada Verdel

    2016-02-01

    Full Text Available The time-dependent role of cations was investigated by ageing four different aqueous solutions of cation chlorides. A linear correlation was found between the cations’ Setchenov coefficient for the salting-out of benzene and the increase in the conductivity with time. The conductivity of the structure-breaking cations or the chaotropes increased more significantly with time than the conductivity of the kosmotropes. Since larger water clusters accelerate the proton or hydroxyl hopping mechanism, we propose that the structuring of the hydration shells of the chaotropes might be spontaneously enhanced over time.

  17. Frontiers in Gold Chemistry

    OpenAIRE

    Ahmed A. Mohamed

    2015-01-01

    Basic chemistry of gold tells us that it can bond to sulfur, phosphorous, nitrogen, and oxygen donor ligands. The Frontiers in Gold Chemistry Special Issue covers gold complexes bonded to the different donors and their fascinating applications. This issue covers both basic chemistry studies of gold complexes and their contemporary applications in medicine, materials chemistry, and optical sensors. There is a strong belief that aurophilicity plays a major role in the unending applications of g...

  18. Simultaneous anionic and cationic redox

    Science.gov (United States)

    Jung, Sung-Kyun; Kang, Kisuk

    2017-12-01

    It is challenging to unlock anionic redox activity, accompanied by full utilization of available cationic redox process, to boost capacity of battery cathodes. Now, material design by tuning the metal-oxygen interaction is shown to be a promising solution.

  19. Gold in plants

    International Nuclear Information System (INIS)

    Girling, C.A.; Peterson, P.J.

    1980-01-01

    Many plants have the ability to take up gold from the soil and to accumulate it in their tisssue. Advances have been made in understanding these processes to the point where their exploitation in the field of prospecting for gold appears practically feasible. Neutron activation analysis is used for the determination of the small quantities of gold in plants

  20. Cation disorder in Ga1212.

    Science.gov (United States)

    Greenwood, K B; Ko, D; Vander Griend, D A; Sarjeant, G M; Milgram, J W; Garrity, E S; DeLoach, D I; Poeppelmeier, K R; Salvador, P A; Mason, T O

    2000-07-24

    Substitution of calcium for strontium in LnSr2-xCaxCu2GaO7 (Ln = La, Pr, Nd, Gd, Ho, Er, Tm, and Yb) materials at ambient pressure and 975 degrees C results in complete substitution of calcium for strontium in the lanthanum and praseodymium systems and partial substitution in the other lanthanide systems. The calcium saturation level depends on the size of the Ln cation, and in all cases, a decrease in the lattice parameters with calcium concentration was observed until a common, lower bound, average A-cation size is reached. Site occupancies from X-ray and neutron diffraction experiments for LnSr2-xCaxCu2GaO7 (x = 0 and x = 2) confirm that the A-cations distribute between the two blocking-layer sites and the active-layer site based on size. A quantitative link between cation distribution and relative site-specific cation enthalpy for calcium, strontium, and lanthanum within the gallate structure is derived. The cation distribution in other similar materials can potentially be modeled.

  1. Polyelectrolyte-modified cowpea mosaic virus for the synthesis of gold nanoparticles.

    Science.gov (United States)

    Aljabali, Alaa A A; Evans, David J

    2014-01-01

    Polyelectrolyte surface-modified cowpea mosaic virus (CPMV) can be used for the templated synthesis of narrowly dispersed gold nanoparticles. Cationic polyelectrolyte, poly(allylamine) hydrochloride, is electrostatically bound to the external surface of the virus capsid. The polyelectrolyte-coated CPMV promotes adsorption of aqueous gold hydroxide anionic species, prepared from gold(III) chloride and potassium carbonate, that are easily reduced to form CPMV-templated gold nanoparticles. The process is simple and environmentally benign using only water as solvent at ambient temperature.

  2. Calcium oxide supported gold nanoparticles as catalysts for the selective epoxidation of styrene by t-butyl hydroperoxide.

    Science.gov (United States)

    Dumbre, Deepa K; Choudhary, Vasant R; Patil, Nilesh S; Uphade, Balu S; Bhargava, Suresh K

    2014-02-01

    Gold nanoparticles are deposited on basic CaO supports as catalysts for the selective conversion of styrene into styrene oxide. Synthetic methods, gold loading and calcination temperatures are varied to permit an understanding of their influence on gold nanoparticle size, the presence of cationic gold species and the nature of interaction between the gold nanoparticles and the CaO support. Based on these studies, optimal conditions are designed to make the Au/CaO catalyst efficient for the selective epoxidation of styrene. Copyright © 2013 Elsevier Inc. All rights reserved.

  3. Gold-Mining

    DEFF Research Database (Denmark)

    Raaballe, J.; Grundy, B.D.

    2002-01-01

      Based on standard option pricing arguments and assumptions (including no convenience yield and sustainable property rights), we will not observe operating gold mines. We find that asymmetric information on the reserves in the gold mine is a necessary and sufficient condition for the existence...... of operating gold mines. Asymmetric information on the reserves in the mine implies that, at a high enough price of gold, the manager of high type finds the extraction value of the company to be higher than the current market value of the non-operating gold mine. Due to this under valuation the maxim of market...

  4. Liquid-solid extraction of cationic metals by cationic amphiphiles

    International Nuclear Information System (INIS)

    Muller, W.

    2010-01-01

    In the field of selective separation for recycling of spent nuclear fuel, liquid-liquid extraction processes are widely used (PUREX, DIAMEX..) in industrial scale. In order to guarantee a sustainable nuclear energy for the forthcoming generations, alternative reprocessing techniques are under development. One of them bases on the studies from Heckmann et al in the 80's and consists in selectively precipitating actinides from aqueous waste solutions by cationic surfactants (liquid-solid extraction). This technique has some interesting advantages over liquid-liquid extraction techniques, because several steps are omitted like stripping or solvent washing. Moreover, the amount of waste is decreased considerably, since no contaminated organic solvent is produced. In this thesis, we have carried out a physico-chemical study to understand the specific interactions between the metallic cations with the cationic surfactant. First, we have analysed the specific effect of the different counter-ions (Cl - , NO 3 - , C 2 O 4 2- ) and then the effect of alkaline cations on the structural properties of the surfactant aggregation in varying thermodynamical conditions. Finally, different multivalent cations (Cu 2+ , Zn 2+ , UO 2 2+ , Fe 3+ , Nd 3+ , Eu 3+ , Th 4+ ) were considered; we have concluded that depending on the anionic complex of these metals formed in acidic media, we can observe either an adsorption at the micellar interface or not. This adsorption has a large influence of the surfactant aggregation properties and determines the limits of the application in term of ionic strength, temperature and surfactant concentration. (author) [fr

  5. Molecular dynamics simulation of cascade damage in gold

    International Nuclear Information System (INIS)

    Alonso, E.; Caturla, M.J.; Tang, M.; Huang, H.; Diaz de la Rubia, T.

    1997-01-01

    High-energy cascades have been simulated in gold using molecular dynamics with a modified embedded atom method potential. The results show that both vacancy and interstitial clusters form with high probability as a result of intracascade processes. The formation of clusters has been interpreted in terms of the high pressures generated in the core of the cascade during the early stages. The authors provide evidence that correlation between interstitial and vacancy clustering exists

  6. Cationic polyhydrido cluster complexes. Crystal and molecular structures of (Ir3(Ph2P(CH2)3PPh2)3(H)7(CO))2+ and (Ir3(Ph2P(CH2)2(2-py))3(H)7)2+

    International Nuclear Information System (INIS)

    Hsienhau Wang; Casalnuovo, A.L.; Johnson, B.J.; Mueting, A.M.; Pignolet, L.H.

    1988-01-01

    Two new cationic polyhydrido cluster complexes of iridium have been synthesized and characterized by single-crystal x-ray diffraction and by ir and 1 H and 31 P NMR spectroscopy (Ir 3 (dppp) 3 (H) 7 (CO)) 2+ (2) and (Ir3 (PN) 3 (H) 7)2+ (5), where dppp = 1,3-bis(diphenylphosphino)propane and PN = 1-(2-pyridyl)-2-(diphenylphosphino)ethane, were synthesized by the reaction of CO with (Ir 3 (dppp) 3 (H) 7 ) 2+ (1) in CH 2 Cl 2 solution and H 2 with (Ir(PN)(COD)) + (4) in CH 3 OH solution, respectively. Crystal structures for both compounds is reported. The hydride positions were not located in the crystal structure analyses but were deduced from structural and 1 H NMR data. The molecular structure of 2 consists of a bilateral triangle of three iridium atoms with a carbonyl at the vertex and a chelating dppp ligand on each iridium atom. 1 H NMR data with use of acetone-d 6 as solvent showed that 2 possesses four doubly bridging hydrides and three terminal hydrides, yielding C 1 symmetry. The molecular structure of 5 consists of an approximately equilateral triangle of three iridium atoms (average Ir-Ir distance 2.746 (1) angstrom) with one PN ligand chelated to each iridium atom. 1 H NMR analysis, with use of CD 2 Cl 2 as solvent, showed that 5 has one triply bridging hydride and six terminal hydrides, giving C 3 symmetry. (Ir 3 (dppp) 3 (H) 7 (CH 3 C 6 H 4 NC)) 2+ (3) a complex structurally analogous to 2, was synthesized from 1 and p-tolyl isocyanide in CH 2 Cl 2 solution and characterized by ir and 1 H and 31 P NMR spectroscopy. 44 refs., 3 figs., 3 tabs

  7. Star-like superalkali cations featuring planar pentacoordinate carbon

    Energy Technology Data Exchange (ETDEWEB)

    Guo, Jin-Chang [Institute of Materials Science and Department of Chemistry, Xinzhou Teachers’ University, Xinzhou, Shanxi 034000 (China); Tian, Wen-Juan; Zhao, Xue-Feng; Wu, Yan-Bo, E-mail: wyb@sxu.edu.cn, E-mail: hj.zhai@sxu.edu.cn, E-mail: lisidian@sxu.edu.cn; Li, Si-Dian, E-mail: wyb@sxu.edu.cn, E-mail: hj.zhai@sxu.edu.cn, E-mail: lisidian@sxu.edu.cn [Nanocluster Laboratory, Institute of Molecular Science, Shanxi University, Taiyuan, Shanxi 030006 (China); Wang, Ying-Jin [Institute of Materials Science and Department of Chemistry, Xinzhou Teachers’ University, Xinzhou, Shanxi 034000 (China); Nanocluster Laboratory, Institute of Molecular Science, Shanxi University, Taiyuan, Shanxi 030006 (China); Zhai, Hua-Jin, E-mail: wyb@sxu.edu.cn, E-mail: hj.zhai@sxu.edu.cn, E-mail: lisidian@sxu.edu.cn [Nanocluster Laboratory, Institute of Molecular Science, Shanxi University, Taiyuan, Shanxi 030006 (China); State Key Laboratory of Quantum Optics and Quantum Optics Devices, Shanxi University, Taiyuan, Shanxi 030006 (China)

    2016-06-28

    Superalkali cations, known to possess low vertical electron affinities (VEAs), high vertical detachment energies, and large highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) energy gaps, are intriguing chemical species. Thermodynamically, such species need to be the global minima in order to serve as the promising targets for experimental realization. In this work, we propose the strategies of polyhalogenation and polyalkalination for designing the superalkali cations. By applying these strategies, the local-minimum planar pentacoordinate carbon (ppC) cluster CBe{sub 5} can be modified to form a series of star-like superalkali ppC or quasi-ppC CBe{sub 5}X{sub 5}{sup +} (X = F, Cl, Br, Li, Na, K) cations containing a CBe{sub 5} moiety. Polyhalogenation and polyalkalination on the CBe{sub 5} unit may help eliminate the high reactivity of bare CBe{sub 5} molecule by covering the reactive Be atoms with noble halogen anions and alkali cations. Computational exploration of the potential energy surfaces reveals that the star-like ppC or quasi-ppC CBe{sub 5}X{sub 5}{sup +} (X = F, Cl, Br, Li, Na, K) clusters are the true global minima of the systems. The predicted VEAs for CBe{sub 5}X{sub 5}{sup +} range from 3.01 to 3.71 eV for X = F, Cl, Br and 2.12–2.51 eV for X = Li, Na, K, being below the lower bound of the atomic ionization potential of 3.89 eV in the periodic table. Large HOMO-LUMO energy gaps are also revealed for the species: 10.76–11.07 eV for X = F, Cl, Br and 4.99–6.91 eV for X = Li, Na, K. These designer clusters represent the first series of superalkali cations with a ppC center. Bonding analyses show five Be–X–Be three-center two-electron (3c-2e) σ bonds for the peripheral bonding, whereas the central C atom is associated with one 6c-2e π bond and three 6c-2e σ bonds, rendering (π and σ) double aromaticity. Born-Oppenheimer molecular dynamics simulations indicate that the CBe{sub 5} motif is robust in the

  8. Cluster-to-cluster transformation among Au6, Au8 and Au11 nanoclusters.

    Science.gov (United States)

    Ren, Xiuqing; Fu, Junhong; Lin, Xinzhang; Fu, Xuemei; Yan, Jinghui; Wu, Ren'an; Liu, Chao; Huang, Jiahui

    2018-05-22

    We present the cluster-to-cluster transformations among three gold nanoclusters, [Au6(dppp)4]2+ (Au6), [Au8(dppp)4Cl2]2+ (Au8) and [Au11(dppp)5]3+ (Au11). The conversion process follows a rule that states that the transformation of a small cluster to a large cluster is achieved through an oxidation process with an oxidizing agent (H2O2) or with heating, while the conversion of a large cluster to a small one occurs through a reduction process with a reducing agent (NaBH4). All the reactions were monitored using UV-Vis spectroscopy and ESI-MS. This work may provide an alternative approach to the synthesis of novel gold nanoclusters and a further understanding of the structural transformation relationship of gold nanoclusters.

  9. Cluster headache

    Science.gov (United States)

    Histamine headache; Headache - histamine; Migrainous neuralgia; Headache - cluster; Horton's headache; Vascular headache - cluster ... Doctors do not know exactly what causes cluster headaches. They ... (chemical in the body released during an allergic response) or ...

  10. Gold and uranium extraction

    International Nuclear Information System (INIS)

    James, G.S.; Davidson, R.J.

    1977-01-01

    A process for extracting gold and uranium from an ore containing them both comprising the steps of pulping the finely comminuted ore with a suitable cyanide solution at an alkaline pH, acidifying the pulp for uranium dissolution, adding carbon activated for gold recovery to the pulp at a suitable stage, separating the loaded activated carbon from the pulp, and recovering gold from the activated carbon and uranium from solution

  11. Gold mineralogy and extraction

    Energy Technology Data Exchange (ETDEWEB)

    Cashion, J.D.; Brown, L.J. [Monash University, Physics Department (Australia)

    1998-12-15

    Several examples are examined in which Moessbauer spectroscopic analysis of gold mineral samples, treated concentrates and extracted species has provided information not obtainable by competing techniques. Descriptions are given of current work on bacterial oxidation of pyritic ores and on the adsorbed species from gold extracted from cyanide and chloride solutions onto activated carbon and polyurethane foams. The potential benefits for the gold mining industry from Moessbauer studies and some limitations on the use of the technique are also discussed.

  12. Gold mineralogy and extraction

    International Nuclear Information System (INIS)

    Cashion, J.D.; Brown, L.J.

    1998-01-01

    Several examples are examined in which Moessbauer spectroscopic analysis of gold mineral samples, treated concentrates and extracted species has provided information not obtainable by competing techniques. Descriptions are given of current work on bacterial oxidation of pyritic ores and on the adsorbed species from gold extracted from cyanide and chloride solutions onto activated carbon and polyurethane foams. The potential benefits for the gold mining industry from Moessbauer studies and some limitations on the use of the technique are also discussed

  13. Spectrophotometric method of the determination of gold (III) by using imipramine hydrochloride and promethazine hydrochloride

    International Nuclear Information System (INIS)

    Dembinski, B.; Kurzawa, M.; Szydlowska-Czerniak, A.

    2003-01-01

    Imipramine hydrochloride (IPM.HCl) and promethazine hydrochloride (PMT-HCl) were used for the spectrophotometric determination of gold (III) in the aqueous solution. The halides complexes of gold (III) created a coloured coupling with the studied drugs which were extractable in chloroform. These new compounds were characterized by IR,UV-VIS spectra and thermal and elemental analysis. Rapid and sensitive spectrophotometric method for the determination of gold (III) in the aqueous solution is described. The absorbance was found to be linear function of the gold (III) concentration in the range from 0.2 to 20 x10/sup -1/ mg. The ratio of complex (AuX/sub 4/) to the organic cation from drug in the obtained compounds was determined as 1:1. The method was satisfactorily applied to the analysis of gold (III). A great advantage of the proposed method is that the trace amounts of gold (III) can also be examined. (author)

  14. Electron attachment and electron ionization of acetic acid clusters embedded in helium nanodroplets

    NARCIS (Netherlands)

    da Silva, F. Ferreira; Jaksch, S.; Martins, G.; Dang, H. M.; Dampc, M.; Denifl, S.; Maerk, T. D.; Limao-Vieira, P.; Liu, J.; Yang, S.; Ellis, A. M.; Scheier, P.

    2009-01-01

    The effect of incident electrons on acetic acid clusters is explored for the first time. The acetic acid clusters are formed inside liquid helium nanodroplets and both cationic and anionic products ejected into the gas phase are detected by mass spectrometry. The cation chemistry (induced by

  15. New double-cation borohydrides

    Energy Technology Data Exchange (ETDEWEB)

    Lindemann, Inge; Domenech Ferrer, Roger; Schultz, Ludwig; Gutfleisch, Oliver [IFW Dresden, Institute for Metallic Materials, P.O. Box 270016, 01171 Dresden (Germany); Filinchuk, Yaroslav [Swiss-Norwegian Beam Lines at ESRF, BP-220, 38043 Grenoble (France); Hagemann, Hans; Cerny, Radovan [Department of Physical Chemistry and Crystallography, University of Geneva, 1211 Geneva (Switzerland)

    2011-07-01

    Complex hydrides are under consideration for on-board hydrogen storage due to their high hydrogen density. However, up to now conventional borohydrides are either too stable or unstable for applications as in PEM fuel cells (60-120 C). Recently, double-cation borohydride systems have attracted great interest. The desorption temperature of the borohydrides decreases with increasing electronegativity of the cation. Consequently, it is possible to tailor a feasible on-board hydrogen storage material by the combination of appropriate cations. The stability was found to be intermediate between the single-cation borohydride systems. Two combinations were sucessfully synthesised by metathesis reaction via high energy ball milling. Al-Li-borohydride shows desorption at about 70 C combined with a very high hydrogen density (17.2 wt.%) and the Na-Al-borohydride (14.2 wt.%) decomposes around 90 C. Both desorption temperatures are in the target range for applications. The decomposition pathways were observed by in-situ-Raman spectroscopy, DSC (Differential Scanning Calorimetry), TG (Thermogravimetry) and thermal desorption measurements.

  16. Geometric, stable and electronic properties of Aun–2Y2 (n = 3–8) clusters

    International Nuclear Information System (INIS)

    Kai-Tian, Qi; Yong, Sheng; Hua-Ping, Mao; Hong-Yan, Wang

    2010-01-01

    Employing first-principles methods, based on the density function theory, and using the LANL2DZ basis sets, the ground-state geometric, the stable and the electronic properties of Au n–2 Y 2 clusters are investigated in this paper. Meanwhile, the differences in property among pure gold clusters, pure yttrium clusters, gold clusters doped with one yttrium atom, and gold clusters doped with two yttrium atoms are studied. We find that when gold clusters are doped by two yttrium atoms, the odd-even oscillatory behaviours of Au n–1 Y and Au n disappear. The properties of Au n–2 Y 2 clusters are close to those of pure yttrium clusters

  17. Random Surface Texturing of Silicon Dioxide Using Gold Agglomerates

    Science.gov (United States)

    2016-07-01

    a visual indicator of the formation of gold clusters on the SiO2 . The glass would make observing a color change in the gold film easier later in the...unlimited. 13. SUPPLEMENTARY NOTES 14. ABSTRACT A fabrication process for creating a silicon dioxide ( SiO2 ) light-trapping structure as part of...even distribution of irregular agglomerates, also known as “complete islanding”. By using these gold agglomerations as a metal mask, the SiO2 can be

  18. Liquid-solid extraction of metallic cations by cationic amphiphiles

    International Nuclear Information System (INIS)

    Mueller, Wolfram; Sievers, Torsten K.; Zemb, Thomas; Diat, Olivier; Sievers, Torsten K.; Dejugnat, Christophe

    2012-01-01

    In the field of selective metal ion separation, liquid-liquid extraction is usually conducted through an emulsion mixing of hydrophobic complexants dispersed in an organic phase and acidic water containing the ionic species. Recently, it has been shown that amphiphilic complexants could influence strongly extraction efficiency by enhancing the interfacial interaction between the metal ion in the aqueous and the complexant in the organic phase. Moreover, these amphiphiles can also substitute the organic phase if an appropriate aliphatic chain is chosen. The dispersion of such amphiphilic complexants in an aqueous solution of salt mixtures is not only attractive for studying specific interactions but also to better the understanding of complex formation in aqueous solution of multivalent metal ions, such as lanthanides and actinides. This understanding is of potential interest for a broad range of industries including purification of rare earth metals and pollute treatment e.g. of fission byproducts. This principle can also be applied to liquid-solid extraction, where the final state of the separation is a solid phase containing the selectively extracted ions. Indeed, a novel solid-liquid extraction method exploits the selective precipitation of metal ions from an aqueous salt mixture using a cationic surfactant, below its Krafft point (temperature below which the long aliphatic chains of surfactant crystallize). This technique has been proven to be highly efficient for the separation of actinides and heavy metal using long chain ammonium or pyridinium amphiphiles. The most important point in this process is the recognition of cationic metal ions by cationic surfactants. By computing the free energy of the polar head group per micelle as a function of the different counter-anions, we have demonstrated for the first time that different interactions exist between the micellar surface and the ions. These interactions depend on the nature of the cation but also on

  19. Monovalent Cation Activation of the Radical SAM Enzyme Pyruvate Formate-Lyase Activating Enzyme.

    Science.gov (United States)

    Shisler, Krista A; Hutcheson, Rachel U; Horitani, Masaki; Duschene, Kaitlin S; Crain, Adam V; Byer, Amanda S; Shepard, Eric M; Rasmussen, Ashley; Yang, Jian; Broderick, William E; Vey, Jessica L; Drennan, Catherine L; Hoffman, Brian M; Broderick, Joan B

    2017-08-30

    Pyruvate formate-lyase activating enzyme (PFL-AE) is a radical S-adenosyl-l-methionine (SAM) enzyme that installs a catalytically essential glycyl radical on pyruvate formate-lyase. We show that PFL-AE binds a catalytically essential monovalent cation at its active site, yet another parallel with B 12 enzymes, and we characterize this cation site by a combination of structural, biochemical, and spectroscopic approaches. Refinement of the PFL-AE crystal structure reveals Na + as the most likely ion present in the solved structures, and pulsed electron nuclear double resonance (ENDOR) demonstrates that the same cation site is occupied by 23 Na in the solution state of the as-isolated enzyme. A SAM carboxylate-oxygen is an M + ligand, and EPR and circular dichroism spectroscopies reveal that both the site occupancy and the identity of the cation perturb the electronic properties of the SAM-chelated iron-sulfur cluster. ENDOR studies of the PFL-AE/[ 13 C-methyl]-SAM complex show that the target sulfonium positioning varies with the cation, while the observation of an isotropic hyperfine coupling to the cation by ENDOR measurements establishes its intimate, SAM-mediated interaction with the cluster. This monovalent cation site controls enzyme activity: (i) PFL-AE in the absence of any simple monovalent cations has little-no activity; and (ii) among monocations, going down Group 1 of the periodic table from Li + to Cs + , PFL-AE activity sharply maximizes at K + , with NH 4 + closely matching the efficacy of K + . PFL-AE is thus a type I M + -activated enzyme whose M + controls reactivity by interactions with the cosubstrate, SAM, which is bound to the catalytic iron-sulfur cluster.

  20. BROOKHAVEN: High energy gold

    International Nuclear Information System (INIS)

    Bleser, Ed

    1992-01-01

    On April 24, Brookhaven's Alternating Gradient Synchrotron (AGS) started to deliver gold ions at 11.4 GeV per nucleon (2,000 GeV per ion) to experimenters who were delighted not only to receive the world's highest energy gold beam but also to receive it on schedule

  1. Thermodynamics and Cation Diffusion in the Oxygen Ion Conductor Lsgm

    Science.gov (United States)

    Martin, M.; Schulz, O.

    Perovskite type oxides based on LaGaO3 are of large technical interest because of their high oxygen-ion conductivity. Lanthanum gallate doped with Sr on A- and Mg on B-sites, La1-xSrxGa1-yMgyO3-(x+y)/2 (LSGM), reaches higher oxygen-ion conductivities than yttria-doped zirconia (YSZ). Thus LSGM represents a promising alternative for YSZ as electrolyte in solid oxide fuel cells (SOFC). Cells using thin LSGM-layers as electrolyte are expected to operate at intermediate temperatures around 700°C for more than 30000 hours without severe degradation. A potential long term degradation effect of LSGM is kinetic demixing of the electrolyte, caused by different cation diffusion coefficients. In this paper we report on experimental studies concerning the phase diagram of LSGM and the diffusion of cations. Cation self-diffusion of 139La, 84Sr and 25Mg and cation impurity diffusion of 144Nd, 89Y and 56Fe in polycrystalline LSGM samples was investigated by secondary ion mass spectrometry (SIMS) for temperatures between 900°C and 1400°C. It was found that diffusion occurs by means of bulk and grain boundaries. The bulk diffusion coefficients are similar for all cations with activation energies which are strongly dependent on temperature. At high temperatures, the activation energies are about 5 eV, while at low temperatures values of about 2 eV are found. These results are explained by a frozen in defect structure at low temperatures. This means that the observed activation energy at low temperatures represents only the migration energy of the different cations while the observed activation energy at high temperatures is the sum of the defect formation energy and the migration energy. The migration energies for all cations are nearly identical, although 139La, 84Sr and 144Nd are occupying A-sites while 25Mg and 56Fe are occupying B-sites in the perovskite-structure. To explain these experimental findings we propose a defect cluster containing cation vacancies in both the A

  2. Tripodal receptors for cation and anion sensors

    NARCIS (Netherlands)

    Kuswandi, Bambang; Nuriman, [Unknown; Verboom, Willem; Reinhoudt, David

    2006-01-01

    This review discusses different types of artificial tripodal receptors for the selectiverecognition and sensing of cations and anions. Examples on the relationship between structure andselectivity towards cations and anions are described. Furthermore, their applications as potentiometricion sensing

  3. Vibrational properties of gold nanoparticles obtained by green synthesis

    Science.gov (United States)

    Alvarez, Ramón A. B.; Cortez-Valadez, M.; Bueno, L. Oscar Neira; Britto Hurtado, R.; Rocha-Rocha, O.; Delgado-Beleño, Y.; Martinez-Nuñez, C. E.; Serrano-Corrales, Luis Ivan; Arizpe-Chávez, H.; Flores-Acosta, M.

    2016-10-01

    This study reports the synthesis and characterization of gold nanoparticles through an ecological method to obtain nanostructures from the extract of the plant Opuntia ficus-indica. Colloidal nanoparticles show sizes that vary between 10-20 nm, and present various geometric morphologies. The samples were characterized through optical absorption, Raman Spectroscopy and Transmission Electron Microscopy (TEM). Additionally, low energy metallic clusters of Aun (n=2-20 atoms) were modeled by computational quantum chemistry. The theoretical results were obtained with Density Functional Theory (DFT). The predicted results of Au clusters show a tendency and are correlated with the experimental results concerning the optical absorption bands and Raman spectroscopy in gold nanoparticles.

  4. Weighted Clustering

    DEFF Research Database (Denmark)

    Ackerman, Margareta; Ben-David, Shai; Branzei, Simina

    2012-01-01

    We investigate a natural generalization of the classical clustering problem, considering clustering tasks in which different instances may have different weights.We conduct the first extensive theoretical analysis on the influence of weighted data on standard clustering algorithms in both...... the partitional and hierarchical settings, characterizing the conditions under which algorithms react to weights. Extending a recent framework for clustering algorithm selection, we propose intuitive properties that would allow users to choose between clustering algorithms in the weighted setting and classify...

  5. Heavy metal cations permeate the TRPV6 epithelial cation channel.

    Science.gov (United States)

    Kovacs, Gergely; Danko, Tamas; Bergeron, Marc J; Balazs, Bernadett; Suzuki, Yoshiro; Zsembery, Akos; Hediger, Matthias A

    2011-01-01

    TRPV6 belongs to the vanilloid family of the transient receptor potential channel (TRP) superfamily. This calcium-selective channel is highly expressed in the duodenum and the placenta, being responsible for calcium absorption in the body and fetus. Previous observations have suggested that TRPV6 is not only permeable to calcium but also to other divalent cations in epithelial tissues. In this study, we tested whether TRPV6 is indeed also permeable to cations such as zinc and cadmium. We found that the basal intracellular calcium concentration was higher in HEK293 cells transfected with hTRPV6 than in non-transfected cells, and that this difference almost disappeared in nominally calcium-free solution. Live cell imaging experiments with Fura-2 and NewPort Green DCF showed that overexpression of human TRPV6 increased the permeability for Ca(2+), Ba(2+), Sr(2+), Mn(2+), Zn(2+), Cd(2+), and interestingly also for La(3+) and Gd(3+). These results were confirmed using the patch clamp technique. (45)Ca uptake experiments showed that cadmium, lanthanum and gadolinium were also highly efficient inhibitors of TRPV6-mediated calcium influx at higher micromolar concentrations. Our results suggest that TRPV6 is not only involved in calcium transport but also in the transport of other divalent cations, including heavy metal ions, which may have toxicological implications. Copyright © 2010 Elsevier Ltd. All rights reserved.

  6. Subcellular localization of alkaline phosphatase in Bacillus licheniformis 749/C by immunoelectron microscopy with colloidal gold

    International Nuclear Information System (INIS)

    Tinglu, G.; Ghosh, A.; Ghosh, B.K.

    1984-01-01

    Subcellular distribution of the alkaline phosphatase of Bacillus licheniformis 749/C was determined by an immunoelectron microscopy method. Anti-alkaline phosphatase antibody labeled with 15- to 18-nm colloidal gold particles (gold-immunoglobulin G [IgG] complex) were used for the study. Both the plasma membrane and cytoplasmic material were labeled with the gold-IgG particles. These particles formed clusters in association with the plasma membrane; in contrast, in the cytoplasm the particles were largely dispersed, and only a few clusters were found. The gold-IgG binding was quantitatively estimated by stereological analysis of labeled, frozen thin sections. This estimation of a variety of control samples showed that the labeling was specific for the alkaline phosphatase. Cluster formation of the gold -IgG particles in association with the plasma membrane suggests that existence of specific alkaline phosphatase binding sites (receptors) in the plasma membrane of B. licheniformis 749/C. 27 references, 6 figures, 1 table

  7. Aqueous gold nanosols stabilized by electrostatic protection generated by X-ray irradiation assisted radical reduction

    International Nuclear Information System (INIS)

    Wang, C.-H.; Hua, Tzu-En; Chien, C.-C.; Yu, Y.-L.; Yang, T.-Y.; Liu, C.-J.; Leng, W.-H.; Hwu, Y.; Yang, Y.-C.; Kim, Chong-Cook; Je, Jung-Ho; Chen, C.-H.; Lin, H.-M.; Margaritondo, G.

    2007-01-01

    Reductant, stabilizer-free colloidal gold solutions were fabricated by a new room-temperature synchrotron X-ray irradiation method. The influence of process parameters such as the pH value and the exposure time on the structure of gold nanoparticles was investigated. The mechanisms underlying the X-ray-triggered reduction of gold ions and the formation of gold clusters are discussed in detail. The X-ray irradiation derived highly concentrated gold nanoparticles are readily to be re-dispersed and possess suitable colloidal stability within cellular environment. The characterization included a study of the possible cytotoxicity for the EMT-6 tumor cell line: the negative results indicate that the gold clusters produced with our approach are biocompatible

  8. Cationic electrodepositable coating composition comprising lignin

    Science.gov (United States)

    Fenn, David; Bowman, Mark P; Zawacky, Steven R; Van Buskirk, Ellor J; Kamarchik, Peter

    2013-07-30

    A cationic electrodepositable coating composition is disclosed. The present invention in directed to a cationic electrodepositable coating composition comprising a lignin-containing cationic salt resin, that comprises (A) the reaction product of: lignin, an amine, and a carbonyl compound; (B) the reaction product of lignin, epichlorohydrin, and an amine; or (C) combinations thereof.

  9. Asymmetric cation-binding catalysis

    DEFF Research Database (Denmark)

    Oliveira, Maria Teresa; Lee, Jiwoong

    2017-01-01

    The employment of metal salts is quite limited in asymmetric catalysis, although it would provide an additional arsenal of safe and inexpensive reagents to create molecular functions with high optical purity. Cation chelation by polyethers increases the salts' solubility in conventional organic...... solvents, thus increasing their applicability in synthesis. The expansion of this concept to chiral polyethers led to the emergence of asymmetric cation-binding catalysis, where chiral counter anions are generated from metal salts, particularly using BINOL-based polyethers. Alkali metal salts, namely KF...... highly enantioselective silylation reactions in polyether-generated chiral environments, and leading to a record-high turnover in asymmetric organocatalysis. This can lead to further applications by the asymmetric use of other inorganic salts in various organic transformations....

  10. Cluster management.

    Science.gov (United States)

    Katz, R

    1992-11-01

    Cluster management is a management model that fosters decentralization of management, develops leadership potential of staff, and creates ownership of unit-based goals. Unlike shared governance models, there is no formal structure created by committees and it is less threatening for managers. There are two parts to the cluster management model. One is the formation of cluster groups, consisting of all staff and facilitated by a cluster leader. The cluster groups function for communication and problem-solving. The second part of the cluster management model is the creation of task forces. These task forces are designed to work on short-term goals, usually in response to solving one of the unit's goals. Sometimes the task forces are used for quality improvement or system problems. Clusters are groups of not more than five or six staff members, facilitated by a cluster leader. A cluster is made up of individuals who work the same shift. For example, people with job titles who work days would be in a cluster. There would be registered nurses, licensed practical nurses, nursing assistants, and unit clerks in the cluster. The cluster leader is chosen by the manager based on certain criteria and is trained for this specialized role. The concept of cluster management, criteria for choosing leaders, training for leaders, using cluster groups to solve quality improvement issues, and the learning process necessary for manager support are described.

  11. Atomistic Modeling of Cation Diffusion in Transition Metal Perovskites La1-xSrxMnO3+/-δfor Solid Oxide Fuel Cell Cathodes Applications

    Science.gov (United States)

    Lee, Yueh-Lin; Duan, Yuhua; Morgan, Dane; Sorescu, Dan; Abernathy, Harry

    Cation diffusion in La1-xSrxMnO3+/-δ (LSM) and in related perovskite materials play an important role in controlling long term performance and stability of solid oxide fuel cell (SOFCs) cathodes. Due to sluggish rates of cation diffusion and complex coupling between defect chemistry and cation diffusion pathways, currently there is still lack of quantitative theoretical model predictions on cation diffusivity vs. T and P(O2) to describe experimental cation tracer diffusivities. In this work, based on ab initio modeling of LSM defect chemistry and migration barriers of the possible cation diffusion pathways, we assess the rates of A-site and B-site cation diffusion in a wide range of T and P(O2) at x =0.0 and 0.2 for SOFC applications. We demonstrate the active cation diffusion pathways in LSM involve cation defect clusters as cation transport carriers, where reduction in the cation migration barriers, which are governed by the steric effect associated with the metal-oxygen cage in the perovskite lattice, is much greater than the penalty of repulsive interaction in the A-site and B-site cation vacancy clusters, leading to higher cation diffusion rates as compared to those of single cation vacancy hopping mechanisms. The predicted Mn and La/Sr cation self-diffusion coefficients of LSM at at x =0.0 and 0.2 along with their 1/T and P(O2) dependences, are in good agreement with the experimental tracer diffusion coefficients.

  12. Medicinal gold compounds

    International Nuclear Information System (INIS)

    Parish, R.V.; Cottrill, S.M.

    1987-01-01

    A major use of gold compounds in the pharmaceutical industry is for anti-arthritic agents. The disease itself is not understood and little is known about the way in which the drugs act, but detailed pictures of the distribution of gold in the body are available, and some of the relevant biochemistry is beginning to emerge. The purpose of this article is to give a survey of the types of compounds presently employed in medicine, of the distribution of gold in the body which results from their use, and of some relevant chemistry. Emphasis is placed on results obtained in the last few years

  13. Structure prediction of AlnOm clusters

    International Nuclear Information System (INIS)

    Smok, P

    2011-01-01

    Genetic algorithm simulations, using Buckingham potential to represent the anion-anion and cation-anion short-range interactions, were performed in order to predict the equilibrium positions of the Al and O ions in Al n O m clusters. In order to find the equilibrium structures of compounds a self-organizing genetic algorithm were constructed. The calculation were carried out for several clusters Al n O m , with different numbers of aluminium and oxygen atoms.

  14. Isotopic clusters

    International Nuclear Information System (INIS)

    Geraedts, J.M.P.

    1983-01-01

    Spectra of isotopically mixed clusters (dimers of SF 6 ) are calculated as well as transition frequencies. The result leads to speculations about the suitability of the laser-cluster fragmentation process for isotope separation. (Auth.)

  15. Cluster Headache

    Science.gov (United States)

    ... a role. Unlike migraine and tension headache, cluster headache generally isn't associated with triggers, such as foods, hormonal changes or stress. Once a cluster period begins, however, drinking alcohol ...

  16. Cluster Headache

    OpenAIRE

    Pearce, Iris

    1985-01-01

    Cluster headache is the most severe primary headache with recurrent pain attacks described as worse than giving birth. The aim of this paper was to make an overview of current knowledge on cluster headache with a focus on pathophysiology and treatment. This paper presents hypotheses of cluster headache pathophysiology, current treatment options and possible future therapy approaches. For years, the hypothalamus was regarded as the key structure in cluster headache, but is now thought to be pa...

  17. Categorias Cluster

    OpenAIRE

    Queiroz, Dayane Andrade

    2015-01-01

    Neste trabalho apresentamos as categorias cluster, que foram introduzidas por Aslak Bakke Buan, Robert Marsh, Markus Reineke, Idun Reiten e Gordana Todorov, com o objetivo de categoriíicar as algebras cluster criadas em 2002 por Sergey Fomin e Andrei Zelevinsky. Os autores acima, em [4], mostraram que existe uma estreita relação entre algebras cluster e categorias cluster para quivers cujo grafo subjacente é um diagrama de Dynkin. Para isto desenvolveram uma teoria tilting na estrutura triang...

  18. Variation of diffusivity with the cation radii in molten salts of ...

    Indian Academy of Sciences (India)

    Abstract. A molecular dynamics study of the dependence of diffusivity of the cation on ionic radii in molten. AgI is reported. ... potential) to carry out molecular dynamics simulations on α-AgI. ..... There is no clustering of these ions. The anionic.

  19. The Gold Standard Programme

    DEFF Research Database (Denmark)

    Neumann, Tim; Rasmussen, Mette; Ghith, Nermin

    2013-01-01

    To evaluate the real-life effect of an evidence-based Gold Standard Programme (GSP) for smoking cessation interventions in disadvantaged patients and to identify modifiable factors that consistently produce the highest abstinence rates.......To evaluate the real-life effect of an evidence-based Gold Standard Programme (GSP) for smoking cessation interventions in disadvantaged patients and to identify modifiable factors that consistently produce the highest abstinence rates....

  20. Gold nanoprobes for theranostics

    Science.gov (United States)

    Panchapakesan, Balaji; Book-Newell, Brittany; Sethu, Palaniappan; Rao, Madhusudhana; Irudayaraj, Joseph

    2011-01-01

    Gold nanoprobes have become attractive diagnostic and therapeutic agents in medicine and life sciences research owing to their reproducible synthesis with atomic level precision, unique physical and chemical properties, versatility of their morphologies, flexibility in functionalization, ease of targeting, efficiency in drug delivery and opportunities for multimodal therapy. This review highlights some of the recent advances and the potential for gold nanoprobes in theranostics. PMID:22122586

  1. Meaningful Clusters

    Energy Technology Data Exchange (ETDEWEB)

    Sanfilippo, Antonio P.; Calapristi, Augustin J.; Crow, Vernon L.; Hetzler, Elizabeth G.; Turner, Alan E.

    2004-05-26

    We present an approach to the disambiguation of cluster labels that capitalizes on the notion of semantic similarity to assign WordNet senses to cluster labels. The approach provides interesting insights on how document clustering can provide the basis for developing a novel approach to word sense disambiguation.

  2. Horticultural cluster

    OpenAIRE

    SHERSTIUK S.V.; POSYLAYEVA K.I.

    2013-01-01

    In the article there are the theoretical and methodological approaches to the nature and existence of the cluster. The cluster differences from other kinds of cooperative and integration associations. Was develop by scientific-practical recommendations for forming a competitive horticultur cluster.

  3. Facts and Fantasies about Gold

    OpenAIRE

    Klement, Joachim

    2015-01-01

    Due to the increasing popularity of gold as an investment the demand for effective risk management techniques for gold investments has increased as well. In this paper we analyze several drivers of the price of gold that have been proposed in the past. Our analysis indicates that short-term volatility of the price of gold remains rather unpredictable with many of the explanations like the fund flows in physical gold ETF either unreliable or unstable over time. Our analysis suggests that there...

  4. The Effect of Voltage Charging on the Transport Properties of Gold Nanotube Membranes.

    Science.gov (United States)

    Experton, Juliette; Martin, Charles R

    2018-05-01

    Porous membranes are used in chemical separations and in many electrochemical processes and devices. Research on the transport properties of a unique class of porous membranes that contain monodisperse gold nanotubes traversing the entire membrane thickness is reviewed here. These gold nanotubes can act as conduits for ionic and molecular transports through the membrane. Because the tubes are electronically conductive, they can be electrochemically charged by applying a voltage to the membrane. How this "voltage charging" affects the transport properties of gold nanotube membranes is the subject of this Review. Experiments showing that voltage charging can be used to reversibly switch the membrane between ideally cation- and anion-transporting states are reviewed. Voltage charging can also be used to enhance the ionic conductivity of gold nanotube membranes. Finally, voltage charging to accomplish electroporation of living bacteria as they pass through gold nanotube membranes is reviewed. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Cation-Coupled Bicarbonate Transporters

    OpenAIRE

    Aalkjaer, Christian; Boedtkjer, Ebbe; Choi, Inyeong; Lee, Soojung

    2014-01-01

    Cation-coupled HCO3− transport was initially identified in the mid-1970s when pioneering studies showed that acid extrusion from cells is stimulated by CO2/HCO3− and associated with Na+ and Cl− movement. The first Na+-coupled bicarbonate transporter (NCBT) was expression-cloned in the late 1990s. There are currently five mammalian NCBTs in the SLC4-family: the electrogenic Na,HCO3-cotransporters NBCe1 and NBCe2 (SLC4A4 and SLC4A5 gene products); the electroneutral Na,HCO3-cotransporter NBCn1 ...

  6. Cation disorder in shocked orthopyroxene.

    Science.gov (United States)

    Dundon, R. W.; Hafner, S. S.

    1971-01-01

    The study of cation distributions over nonequivalent lattice sites in minerals may reveal information on the history of temperature and pressure in rocks. Chemically homogeneous orthopyroxene specimens were shocked under well-controlled conditions in the laboratory in order to provide a basis for the interpretation of more complex natural materials. As a result of the investigation it is concluded that the distribution of magnesium and iron over the M1 and M2 positions in Bamle enstatite shocked at 1 megabar is highly disordered. It corresponds to an equilibrium distribution of at least 1000 C.

  7. Cation coordination in oxychloride glasses

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, J A [Energy Technology Division, Argonne National Laboratory, Argonne, IL (United States); Holland, D [Physics Department, Warwick University, Coventry (United Kingdom); Bland, J [Physics Department, University of Liverpool, PO Box 147, Liverpool (United Kingdom); Johnson, C E [Physics Department, Northern Illinois University, DeKalb, IL (United States); Thomas, M F [Physics Department, University of Liverpool, PO Box 147, Liverpool (United Kingdom)

    2003-02-19

    Glasses containing mixtures of cations and anions of nominal compositions [Sb{sub 2}O{sub 3}]{sub x} - [ZnCl{sub 2}]{sub 1-x} where x = 0.25, 0.50, 0.75, and 1.00, have been studied by means of neutron diffraction and Raman and Moessbauer spectroscopy. There is preferential bonding within the system with the absence of Sb-Cl bonds. Antimony is found to be threefold coordinated to oxygen, and zinc fourfold coordinated. The main contributing species are of the form [Sb(OSb){sub 2}(OZn)] and [Zn(ClZn){sub 2}(OSb){sub 2}].

  8. Cation coordination in oxychloride glasses

    International Nuclear Information System (INIS)

    Johnson, J A; Holland, D; Bland, J; Johnson, C E; Thomas, M F

    2003-01-01

    Glasses containing mixtures of cations and anions of nominal compositions [Sb 2 O 3 ] x - [ZnCl 2 ] 1-x where x = 0.25, 0.50, 0.75, and 1.00, have been studied by means of neutron diffraction and Raman and Moessbauer spectroscopy. There is preferential bonding within the system with the absence of Sb-Cl bonds. Antimony is found to be threefold coordinated to oxygen, and zinc fourfold coordinated. The main contributing species are of the form [Sb(OSb) 2 (OZn)] and [Zn(ClZn) 2 (OSb) 2

  9. Cluster Matters

    DEFF Research Database (Denmark)

    Gulati, Mukesh; Lund-Thomsen, Peter; Suresh, Sangeetha

    2018-01-01

    sell their products successfully in international markets, but there is also an increasingly large consumer base within India. Indeed, Indian industrial clusters have contributed to a substantial part of this growth process, and there are several hundred registered clusters within the country...... of this handbook, which focuses on the role of CSR in MSMEs. Hence we contribute to the literature on CSR in industrial clusters and specifically CSR in Indian industrial clusters by investigating the drivers of CSR in India’s industrial clusters....

  10. The Free Tricoordinated Silyl Cation Problem

    Directory of Open Access Journals (Sweden)

    Čičak, H.

    2010-03-01

    Full Text Available As the importance and abundance of silicon in our environment is large, it has been thought that silicon might take the place of carbon in forming a host of similar compounds and silicon-based life. However, until today there is no experimental evidence for such a hypothesis and carbon is still unique among the elements in the vast number and variety of compounds it can form. Also, the corresponding derivatives of the two elements show considerable differences in their chemical properties.The essential debate concerning organosilicon chemistry relates to the existence of the free planar tricoordinated silyl cations in condensed phase (R3Si+, in analogy to carbocations (R3C+ which have been known and characterized as free species. Although silyl cations are thermodynamically more stable than their carbon analogs, they are very reactive due to their high inherent electrophilicity and the ability of hypervalent coordination. On the other hand, stabilization by inductive and hyperconjugative effects and larger steric effects of carbocations make them less sensitive to solvation or other environmental effects than silyl cations. Hence, observation of free silyl cations in the condensed phase proved extremely difficult and the actual problem is the question of the degree of the (remaining silyl cation character.The first free silyl cation, trimesitylsilyl cation, and in analogy with it tridurylsilyl cation, were synthesized by Lambert et al. Free silyl cations based on analogy to aromatic ions (homocyclopropenylium and tropylium have also been prepared. However, in these silyl cations the cationic character is reduced by internal π -conjugation. Čičak et al. prepared some silyl-cationic intermediates (Me3Si--CH≡CR+in solid state. With the help of quantum-mechanical calculations it was concluded that these adducts have much more silyl cation than carbocation character.

  11. Isolated single-molecule magnets on native gold.

    Science.gov (United States)

    Zobbi, Laura; Mannini, Matteo; Pacchioni, Mirko; Chastanet, Guillaume; Bonacchi, Daniele; Zanardi, Chiara; Biagi, Roberto; Del Pennino, Umberto; Gatteschi, Dante; Cornia, Andrea; Sessoli, Roberta

    2005-03-28

    The incorporation of thioether groups in the structure of a Mn12 single-molecule magnet, [Mn12(O12)(L)16(H2O)4] with L = 4-(methylthio)benzoate, is a successful route to the deposition of well-separated clusters on native gold surfaces and to the addressing of individual molecules by scanning tunnelling microscopy.

  12. Dendritic functionalization of monolayer-protected gold nanoparticles

    International Nuclear Information System (INIS)

    Cutler, Erin C.; Lundin, Erik; Garabato, B. Davis; Choi, Daeock; Shon, Young-Seok

    2007-01-01

    This paper describes the facile synthesis of nanoparticle-cored dendrimers (NCDs) and nanoparticle megamers from monolayer-protected gold clusters using either single or multi-step reactions. First, 11-mercaptoundecanoic acid/hexanethiolate-protected gold clusters were synthesized using the Schiffrin reaction followed by the ligand place-exchange reaction. A convergent approach for the synthesis of nanoparticle-cored dendrimers uses a single step reaction that is an ester coupling reaction of hydroxy-functionalized dendrons with carboxylic acid-functionalized gold clusters. A divergent approach, which is based on multi-step reactions, employs the repetition of an amide coupling reaction and a Michael addition reaction to build polyamidoamine dendritic architectures around a nanoparticle core. Nanoparticle megamers, which are large dendrimer-induced nanoparticle aggregates with an average diameter of more than 300 nm, were prepared by the amide coupling reaction between polyamiodoamine [G-2] dendrimers and carboxylic acid-functionalized gold clusters. 1 H NMR spectroscopy, FT-IR spectroscopy, thermogravimetric analysis (TGA), and transmission electron microscopy (TEM) were used for the characterization of these hybrid nanoparticles

  13. Single pass kernel k-means clustering method

    Indian Academy of Sciences (India)

    In unsupervised classification, kernel -means clustering method has been shown to perform better than conventional -means clustering method in ... 518501, India; Department of Computer Science and Engineering, Jawaharlal Nehru Technological University, Anantapur College of Engineering, Anantapur 515002, India ...

  14. Biosynthesis of gold nanoparticles using diatoms-silica-gold and EPS-gold bionanocomposite formation

    OpenAIRE

    Schröfel, Adam; Kratošová, Gabriela; Bohunická, Markéta; Dobročka, Edmund; Vávra, Ivo

    2011-01-01

    Novel synthesis of gold nanoparticles, EPS-gold, and silica-gold bionanocomposites by biologically driven processes employing two diatom strains (Navicula atomus, Diadesmis gallica) is described. Transmission electron microscopy (TEM) and electron diffraction analysis (SAED) revealed a presence of gold nanoparticles in the experimental solutions of the diatom culture mixed with tetrachloroaureate. Nature of the gold nanoparticles was confirmed by X-ray diffraction studies. Scanning electron m...

  15. ADSORPTION METHOD FOR SEPARATING METAL CATIONS

    Science.gov (United States)

    Khym, J.X.

    1959-03-10

    The chromatographic separation of fission product cations is discussed. By use of this method a mixture of metal cations containing Zr, Cb, Ce, Y, Ba, and Sr may be separated from one another. Mentioned as preferred exchange adsorbents are resins containing free sulfonic acid groups. Various eluants, such as tartaric acid, HCl, and citric acid, used at various acidities, are employed to effect the selective elution and separation of the various fission product cations.

  16. Electronic spectra of astrophysically interesting cations

    Energy Technology Data Exchange (ETDEWEB)

    Maier, John P., E-mail: j.p.maier@unibas.ch; Rice, Corey A., E-mail: j.p.maier@unibas.ch; Mazzotti, Fabio J., E-mail: j.p.maier@unibas.ch; Johnson, Anatoly, E-mail: j.p.maier@unibas.ch [Department of Chemistry, University of Basel, Klingelbergstr. 80, CH-4056 Basel (Switzerland)

    2015-01-22

    The electronic spectra of polyacetylene cations were recorded at 20K in the laboratory in an ion trap instrument. These can then be compared with diffuse interstellar band (DIB) absorptions. Examination of recently published data shows that the attribution of a weak DIB at ∼506.9 nm to diacetylene cation is not justified. Study of the higher excited electronic states of polyacetylene cations shows that their widths can still be sufficiently narrow for consideration as DIB carriers.

  17. Uranium isotope separation using styrene cation exchangers

    International Nuclear Information System (INIS)

    Kahovec, J.

    1980-01-01

    The separation of 235 U and 238 U isotopes is carried out either by simple isotope exchange in the system uranium-cation exchanger (sulphonated styrene divinylbenzene resin), or by combination of isotope exchange in a uranium-cation exchanger (Dowex 50, Amberlite IR-120) system and a chemical reaction. A review is presented of elution agents used, the degree of cation exchanger cross-linking, columns length, and 235 U enrichment. The results are described of the isotope effect study in a U(IV)-U(VI)-cation exchanger system conducted by Japanese and Romanian authors (isotope exchange kinetics, frontal analysis, reverse (indirect) frontal analysis). (H.S.)

  18. Cation-π interactions in structural biology

    OpenAIRE

    Gallivan, Justin P.; Dougherty, Dennis A.

    1999-01-01

    Cation-pi interactions in protein structures are identified and evaluated by using an energy-based criterion for selecting significant sidechain pairs. Cation-pi interactions are found to be common among structures in the Protein Data Bank, and it is clearly demonstrated that, when a cationic sidechain (Lys or Arg) is near an aromatic sidechain (Phe, Tyr, or Trp), the geometry is biased toward one that would experience a favorable cation-pi interaction. The sidechain of Arg is more likely tha...

  19. Simultaneous anion and cation mobility in polypyrrole

    DEFF Research Database (Denmark)

    Skaarup, Steen; Bay, Lasse; Vidanapathirana, K.

    2003-01-01

    and the expulsion of anions; a broad anodic peak centered at ca. - 0.5 V representing the expulsion of cations; and a second broad peak at +0.2 to +0.5 V corresponding to anions being inserted. Although the motion of cations is the most important, as expected, there is a significant anion contribution, thereby...... complicating reproducibility when employing PPy(DBS) polymers as actuators. When the cation is doubly charged, it enters the film less readily, and anions dominate the mobility. Using a large and bulky cation switches the mechanism to apparently total anion motion. The changes in area of the three peaks...

  20. Data Clustering

    Science.gov (United States)

    Wagstaff, Kiri L.

    2012-03-01

    On obtaining a new data set, the researcher is immediately faced with the challenge of obtaining a high-level understanding from the observations. What does a typical item look like? What are the dominant trends? How many distinct groups are included in the data set, and how is each one characterized? Which observable values are common, and which rarely occur? Which items stand out as anomalies or outliers from the rest of the data? This challenge is exacerbated by the steady growth in data set size [11] as new instruments push into new frontiers of parameter space, via improvements in temporal, spatial, and spectral resolution, or by the desire to "fuse" observations from different modalities and instruments into a larger-picture understanding of the same underlying phenomenon. Data clustering algorithms provide a variety of solutions for this task. They can generate summaries, locate outliers, compress data, identify dense or sparse regions of feature space, and build data models. It is useful to note up front that "clusters" in this context refer to groups of items within some descriptive feature space, not (necessarily) to "galaxy clusters" which are dense regions in physical space. The goal of this chapter is to survey a variety of data clustering methods, with an eye toward their applicability to astronomical data analysis. In addition to improving the individual researcher’s understanding of a given data set, clustering has led directly to scientific advances, such as the discovery of new subclasses of stars [14] and gamma-ray bursts (GRBs) [38]. All clustering algorithms seek to identify groups within a data set that reflect some observed, quantifiable structure. Clustering is traditionally an unsupervised approach to data analysis, in the sense that it operates without any direct guidance about which items should be assigned to which clusters. There has been a recent trend in the clustering literature toward supporting semisupervised or constrained

  1. A non-diazo approach to α-oxo gold carbenes via gold-catalyzed alkyne oxidation.

    Science.gov (United States)

    Zhang, Liming

    2014-03-18

    For the past dozen years, homogeneous gold catalysis has evolved from a little known topic in organic synthesis to a fully blown research field of significant importance to synthetic practitioners, due to its novel reactivities and reaction modes. Cationic gold(I) complexes are powerful soft Lewis acids that can activate alkynes and allenes toward efficient attack by nucleophiles, leading to the generation of alkenyl gold intermediates. Some of the most versatile aspects of gold catalysis involve the generation of gold carbene intermediates, which occurs through the approach of an electrophile to the distal end of the alkenyl gold moiety, and their diverse transformations thereafter. On the other hand, α-oxo metal carbene/carbenoids are highly versatile intermediates in organic synthesis and can undergo various synthetically challenging yet highly valuable transformations such as C-H insertion, ylide formation, and cyclopropanation reactions. Metal-catalyzed dediazotizations of diazo carbonyl compounds are the principle and most reliable strategy to access them. Unfortunately, the substrates contain a highly energetic diazo moiety and are potentially explosive. Moreover, chemists need to use energetic reagents to prepare them, putting further constrains on operational safety. In this Account, we show that the unique access to the gold carbene species in homogeneous gold catalysis offers an opportunity to generate α-oxo gold carbenes if both nucleophile and electrophile are oxygen. Hence, this approach would enable readily available and safer alkynes to replace hazardous α-diazo carbonyl compounds as precursors in the realm of gold carbene chemistry. For the past several years, we have demonstrated that alkynes can indeed effectively serve as precursors to versatile α-oxo gold carbenes. In our initial study, we showed that a tethered sulfoxide can be a suitable oxidant, which in some cases leads to the formation of α-oxo gold carbene intermediates. The

  2. A Non-Diazo Approach to α-Oxo Gold Carbenes via Gold-Catalyzed Alkyne Oxidation

    Science.gov (United States)

    2015-01-01

    For the past dozen years, homogeneous gold catalysis has evolved from a little known topic in organic synthesis to a fully blown research field of significant importance to synthetic practitioners, due to its novel reactivities and reaction modes. Cationic gold(I) complexes are powerful soft Lewis acids that can activate alkynes and allenes toward efficient attack by nucleophiles, leading to the generation of alkenyl gold intermediates. Some of the most versatile aspects of gold catalysis involve the generation of gold carbene intermediates, which occurs through the approach of an electrophile to the distal end of the alkenyl gold moiety, and their diverse transformations thereafter. On the other hand, α-oxo metal carbene/carbenoids are highly versatile intermediates in organic synthesis and can undergo various synthetically challenging yet highly valuable transformations such as C–H insertion, ylide formation, and cyclopropanation reactions. Metal-catalyzed dediazotizations of diazo carbonyl compounds are the principle and most reliable strategy to access them. Unfortunately, the substrates contain a highly energetic diazo moiety and are potentially explosive. Moreover, chemists need to use energetic reagents to prepare them, putting further constrains on operational safety. In this Account, we show that the unique access to the gold carbene species in homogeneous gold catalysis offers an opportunity to generate α-oxo gold carbenes if both nucleophile and electrophile are oxygen. Hence, this approach would enable readily available and safer alkynes to replace hazardous α-diazo carbonyl compounds as precursors in the realm of gold carbene chemistry. For the past several years, we have demonstrated that alkynes can indeed effectively serve as precursors to versatile α-oxo gold carbenes. In our initial study, we showed that a tethered sulfoxide can be a suitable oxidant, which in some cases leads to the formation of α-oxo gold carbene intermediates. The

  3. Design and synthesis of magnetic nanoparticles with gold shells for single particle optical tracking

    Science.gov (United States)

    Lim, Jitkang

    The design, synthesis, and characterization of iron oxide core, gold shell nanoparticles are studied in this thesis. Firstly, nanoparticles with 18 +/- 1.7 nm diameter iron oxide cores with ˜5 nm thick gold shells were synthesized via a new seed-mediated electroless deposition method. The nanoparticles were superparamagnetic at room temperature and could be reversibly collected by a permanent magnet. These nanoparticles displayed a sharp localized surface plasmon resonance peak at 605 nm, as predicted by scattering theory, and their large scattering cross-section allowed them to be individually resolved in darkfield optical microscopy while undergoing Brownian motion in aqueous suspension. Later, commercially available 38 +/- 3.8 nm diameter spherical iron oxide nanoparticles (from Ocean Nanotech, Inc) were employed to make core-shell particles. These particles were decorated with cationic poly(diallyldimethylammonium chloride) (PDDA) which further promotes the attachment of small gold clusters. After gold seeding, the average hydrodynamic diameter of the core-shell particles is 172 +/- 65.9 nm. The magnetophoretic motion of these particles was guided by a piece of magnetized mu-metal. Individual particle trajectories were observed by darkfield optical microscopy. The typical magnetophoretic velocity achieved was within the range of 1--10 mum/sec. Random walk analysis performed on these particles while undergoing Brownian motion confirmed that individual particles were indeed being imaged. The particle size variation within the observed sample obtained through random walk analysis was within the size distribution obtained by dynamic light scattering. When the current to the solenoid used to magnetize the mu-metal was turned off, all the collected core-shell particles were readily redispersed by diffusion back into the surrounding environment. A Peclet number analysis was performed to probe the convective motion of nanospheres and nanorods under the influence of

  4. Cluster evolution

    International Nuclear Information System (INIS)

    Schaeffer, R.

    1987-01-01

    The galaxy and cluster luminosity functions are constructed from a model of the mass distribution based on hierarchical clustering at an epoch where the matter distribution is non-linear. These luminosity functions are seen to reproduce the present distribution of objects as can be inferred from the observations. They can be used to deduce the redshift dependence of the cluster distribution and to extrapolate the observations towards the past. The predicted evolution of the cluster distribution is quite strong, although somewhat less rapid than predicted by the linear theory

  5. GOLD IS EARNED FROM THE PRODUCTION OF THAI GOLD LEAF

    Directory of Open Access Journals (Sweden)

    Dirk Bax

    2010-06-01

    Full Text Available Thai people like to cover sacred objects or things dear to them with gold leaf.. Statues of Buddha are sometimes covered with so many layers of gold leaf that they become formless figures, that can hardly be recognized. Portraits of beloved ancestors, statues of elephants and grave tombs are often covered with gold leaf. If one considers the number of Thai people and the popularity of the habit, the amount of gold involved could be considerable.

  6. Afrikaans Syllabification Patterns

    Directory of Open Access Journals (Sweden)

    Tilla Fick

    2010-01-01

    Full Text Available In contrast to English, automatic hyphenation by computer of Afrikaans words is a problem that still needs to be addressed, since errors are still often encountered in printed text. An initial step in this task is the ability to automatically syllabify words. Since new words are created continuously by joining words, it is necessary to develop an “intelligent” technique for syllabification. As a first phase of the research, we consider only the orthographic information of words, and disregard both syntactic and morphological information. This approach allows us to use machine-learning techniques such as artificial neural networks and decision trees that are known for their pattern recognition abilities. Both these techniques are trained with isolated patterns consisting of input patterns and corresponding outputs (or targets that indicate whether the input pattern should be split at a certain position, or not. In the process of compiling a list of syllabified words from which to generate training data for the  syllabification problem, irregular patterns were identified. The same letter patterns are split differently in different words and complete words that are spelled identically are split differently due to meaning. We also identified irregularities in and between  the different dictionaries that we used. We examined the influence range of letters that are involved in irregularities. For example, for their in agter-ente and vaste-rente we have to consider three letters to the left of r to be certain where the hyphen should be inserted. The influence range of the k in verstek-waarde and kleinste-kwadrate is four to the left and three to the right. In an analysis of letter patterns in Afrikaans words we found that the letter e has the highest frequency overall (16,2% of all letters in the word list. The frequency of words starting with s is the highest, while the frequency of words ending with e is the highest. It is important to

  7. Influence of the graphene substrate on morphology of the gold thin film. Spectroscopic ellipsometry study

    International Nuclear Information System (INIS)

    Kostruba, A.M.

    2013-01-01

    In metal optics gold assumes a special status because of its practical importance in optoelectronic and nanooptical devices, and its role huge increases when occurs combination of gold with two-dimension materials. We performed spectroscopic ellipsometry measurements on evaporated gold, and gold–graphene nanostructures to determine the optical dielectric function across a broad spectral range from 250 to 1000 nm. It was found that the deposition of gold film on the quartz substrate covered by graphene flake leads to significant changes in structural and dielectric properties of thin gold layer. Such changes can be explained by increasing of the gold cluster size. The model fit of the ellipsometric data demonstrates that the bilayer “graphene-gold” nanostructure can be described as a uniform optically homogeneous layer with modified optical properties. We can suggest that graphene flake creates a matrix for epitaxial alignment of the crystalline structure of the gold film during its growing. Effective doping of the graphene by free electrons of the gold clusters tends to decrease the optical contrast at the graphene-gold interface.

  8. Gold film with gold nitride - A conductor but harder than gold

    International Nuclear Information System (INIS)

    Siller, L.; Peltekis, N.; Krishnamurthy, S.; Chao, Y.; Bull, S.J.; Hunt, M.R.C.

    2005-01-01

    The formation of surface nitrides on gold films is a particularly attractive proposition, addressing the need to produce harder, but still conductive, gold coatings which reduce wear but avoid the pollution associated with conventional additives. Here we report production of large area gold nitride films on silicon substrates, using reactive ion sputtering and plasma etching, without the need for ultrahigh vacuum. Nanoindentation data show that gold nitride films have a hardness ∼50% greater than that of pure gold. These results are important for large-scale applications of gold nitride in coatings and electronics

  9. 197 Au Mössbauer study of the gold species adsorbed on carbon from cyanide solutions

    Science.gov (United States)

    Kongolo, K.; Bahr, A.; Friedl, J.; Wagner, F. E.

    1990-04-01

    The gold species present on activated carbon after adsorption from solutions of Au(CN)2 - have been studied by197Au Mössbauer spectroscopy as a function of the pH value of the solution, the loading of the carbon, the coadsorption of polyvalent cations, and the treatment of the samples after adsorption. The gold was found to be adsorbed mainly as Au(CN)2 -. Coadsorbed polyvalent cations (Ca²+, Gd³+) have no influence on the Mössbauer parameters of the adsorbed gold complex. After adsorption from acidic solutions (pH ≲ 4), one finds a substantial amount of adsorbed gold with Mössbauer parameters similar to those of crystalline AuCN. Presumably, this gold is bound in Aux(CN)x+1 oligomers which form during drying. An additional product with Mössbauer parameters close to those of KAu(CN)2Cl2 was observed on dried samples after adsorption at pH 1. A minor gold species with an uncommonly small electric quadrupole splitting was found on wet carbons but disappeared on drying.

  10. Activated carbons and gold

    International Nuclear Information System (INIS)

    McDougall, G.J.; Hancock, R.D.

    1980-01-01

    The literature on activated carbon is reviewed so as to provide a general background with respect to the effect of source material and activation procedure on carbon properties, the structure and chemical nature of the surface of the activated carbon, and the nature of absorption processes on carbon. The various theories on the absorption of gold and silver from cyanide solutions are then reviewed, followed by a discussion of processes for the recovery of gold and silver from cyanide solutions using activated carbon, including a comparison with zinc precipitation

  11. Electronic Absorption and MCD Spectra for Pd(AuPPh(3))(8)(2+), Pt(AuPPh(3))(8)(2+), and Related Platinum-Centered Gold Cluster Complexes.

    Science.gov (United States)

    Adrowski, Michael J.; Mason, W. Roy

    1997-03-26

    Electronic absorption and 7.0 T magnetic circular dichroism (MCD) spectra in the UV-vis region, 1.6 to approximately 4.0 &mgr;m(-)(1) (1 &mgr;m(-)(1) = 10(4) cm(-)(1)) are reported for [Pd(AuPPh(3))(8)](NO(3))(2) and [Pt(AuPPh(3))(8)](NO(3))(2) in acetonitrile solutions at room temperature. The MCD spectra are better resolved than the absorption spectra and consist of both A and B terms. The spectra are interpreted in terms of D(4)(d)() skeletal geometry and MO's that are approximated by 5s and 6s orbitals for Pd and Pt/Au atoms, respectively. The lowest energy excited configurations and states are attributed to intraframework (IF) Au(8)(2+) transitions. Evidence is also presented for Pt 5d --> Au 6s transitions in the MCD spectra for Pt(AuPPh(3))(8)(2+). Acetonitrile solution absorption and MCD spectra for the related Pt-centered cluster complexes [Pt(CO)(AuPPh(3))(8)](NO(3))(2), [Pt(AuP(p-tolyl)(3))(8)](NO(3))(2), [Pt(CuCl)(AuPPh(3))(8)](NO(3))(2), [Pt(AgNO(3))(AuPPh(3))(8)](NO(3))(2), [Pt(Hg)(2)(AuPPh(3))(8)](NO(3))(2), [Pt(HgCl)(2)(AuPPh(3))(8)](BF(4))(2), and [Pt(HgNO(3))(2)(AuPPh(3))(8)](BF(4))(2) are also reported and interpreted within the context of the model developed for the M(AuPPh(3))(8)(2+) complexes.

  12. Pinning of size-selected gold and nickel nanoclusters on graphite

    NARCIS (Netherlands)

    Di Vece, M.|info:eu-repo/dai/nl/248753355; Paloma, S.; Palmer, R.E.

    2005-01-01

    Size-selected gold and nickel nanoclusters are of interest from an electronic, catalytic, and biological point of view. These applications require the deposition of the clusters on a surface, and a key challenge is to retain the cluster size. Here controlled energy impact is used to immobilize the

  13. Cationic Dimyristoylphosphatidylcholine and Dioleoyloxytrimethylammonium Propane Lipid Bilayers: Atomistic Insight for Structure and Dynamics

    DEFF Research Database (Denmark)

    Zhao, W.; Gurtovenko, A. A.; Vattulainen, I.

    2012-01-01

    We performed atomistic molecular dynamics simulations of lipid bilayers consisting of a mixture of cationic dioleoyloxytrimethylammonium propane (DOTAP) and zwitterionic dimyristoylphosphatidylcholine (DMPC) lipids at different DOTAP fractions. Our primary focus was the specific effects...... of unsaturated lipid chains on structural and dynamic properties of mixed cationic bilayers. The bilayer area, as well as the ordering of lipid tails, shows a pronounced nonmonotonic behavior when TAP lipid fraction increases. The minimum in area (maximum in ordering) was observed for a bilayer with TAP fraction...... lipids, which were found to form PC-PC and PC-TAP pairs, and the formation of lipid clusters....

  14. Pulsed EPR for studying silver clusters

    International Nuclear Information System (INIS)

    Michalik, J.; Wasowicz, T.; Sadlo, J.; Reijerse, E.J.; Kevan, L.

    1996-01-01

    The cationic silver clusters of different nuclearity have been produced by radiolysis of zeolite A and SAPO molecular sieves containing Ag + as exchangeable cations. The pulsed EPR spectroscopy has been applied for studying the local environment of silver cluster in order to understand the mechanism of cluster formation and stabilization. the electron spin echo modulation (ESEM) results on Ag 6 n+ cluster in dehydration zeolite A indicate that the hexameric silver is stabilized only in sodalite cages which are surrounded by α-cages containing no water molecules. Trimeric silver clusters formed in hydrated A zeolites strongly interact with water, thus the paramagnetic center can be considered as a cluster-water adduct. In SAPO-molecular sieves, silver clusters are formed only in the presence of adsorbed alcohol molecules. From ESEM it is determined that Ag 4 n+ in SAPO-42 is stabilized in α cages, where it is directly coordinated by two methanol molecules. Dimeric silver, Ag 2 + in SAPO-5 and SAPO-11 is located in 6-ring channels and interacts with three CH 3 OH molecules, each in different 10 ring or 12 ring channels. The differences of Ag 2 + stability in SAPO-5 and SAPO-11 are also discussed. (Author)

  15. Cationic polymers and their therapeutic potential

    NARCIS (Netherlands)

    Samal, S.K.; Dash, M.; van Vlierberghe, S.; Kaplan, D.; Chiellini, E.; van Blitterswijk, Clemens; Moroni, Lorenzo; Dubruel, P.

    2012-01-01

    The last decade has witnessed enormous research focused on cationic polymers. Cationic polymers are the subject of intense research as non-viral gene delivery systems, due to their flexible properties, facile synthesis, robustness and proven gene delivery efficiency. Here, we review the most recent

  16. Tripodal Receptors for Cation and Anion Sensors

    Directory of Open Access Journals (Sweden)

    David N. Reinhoudt

    2006-08-01

    Full Text Available This review discusses different types of artificial tripodal receptors for the selectiverecognition and sensing of cations and anions. Examples on the relationship between structure andselectivity towards cations and anions are described. Furthermore, their applications as potentiometricion sensing are emphasised, along with their potential applications in optical sensors or optodes.

  17. Asymmetric Aminalization via Cation-Binding Catalysis

    DEFF Research Database (Denmark)

    Park, Sang Yeon; Liu, Yidong; Oh, Joong Suk

    2018-01-01

    Asymmetric cation-binding catalysis, in principle, can generate "chiral" anionic nucleophiles, where the counter cations are coordinated within chiral environments. Nitrogen-nucleophiles are intrinsically basic, therefore, its use as nucleophiles is often challenging and limiting the scope of the...

  18. Structural and energetic study of cation-π-cation interactions in proteins.

    Science.gov (United States)

    Pinheiro, Silvana; Soteras, Ignacio; Gelpí, Josep Lluis; Dehez, François; Chipot, Christophe; Luque, F Javier; Curutchet, Carles

    2017-04-12

    Cation-π interactions of aromatic rings and positively charged groups are among the most important interactions in structural biology. The role and energetic characteristics of these interactions are well established. However, the occurrence of cation-π-cation interactions is an unexpected motif, which raises intriguing questions about its functional role in proteins. We present a statistical analysis of the occurrence, composition and geometrical preferences of cation-π-cation interactions identified in a set of non-redundant protein structures taken from the Protein Data Bank. Our results demonstrate that this structural motif is observed at a small, albeit non-negligible frequency in proteins, and suggest a preference to establish cation-π-cation motifs with Trp, followed by Tyr and Phe. Furthermore, we have found that cation-π-cation interactions tend to be highly conserved, which supports their structural or functional role. Finally, we have performed an energetic analysis of a representative subset of cation-π-cation complexes combining quantum-chemical and continuum solvation calculations. Our results point out that the protein environment can strongly screen the cation-cation repulsion, leading to an attractive interaction in 64% of the complexes analyzed. Together with the high degree of conservation observed, these results suggest a potential stabilizing role in the protein fold, as demonstrated recently for a miniature protein (Craven et al., J. Am. Chem. Soc. 2016, 138, 1543). From a computational point of view, the significant contribution of non-additive three-body terms challenges the suitability of standard additive force fields for describing cation-π-cation motifs in molecular simulations.

  19. ['Gold standard', not 'golden standard'

    NARCIS (Netherlands)

    Claassen, J.A.H.R.

    2005-01-01

    In medical literature, both 'gold standard' and 'golden standard' are employed to describe a reference test used for comparison with a novel method. The term 'gold standard' in its current sense in medical research was coined by Rudd in 1979, in reference to the monetary gold standard. In the same

  20. Spectroscopic diagnostic of gold plasma

    International Nuclear Information System (INIS)

    Busquet, M.

    1986-01-01

    Results of a simulation of a gold-aluminium alloy target irradiated by laser are presented. FCI code has been used with a processing out of LTE of atomic physics of gold and of multigroup photonics. Emission and reabsorption of gold and aluminium lines are included [fr

  1. Spectroscopic diagnostic of gold plasma

    Energy Technology Data Exchange (ETDEWEB)

    Busquet, M.

    1986-06-01

    Results of a simulation of a gold-aluminium alloy target irradiated by laser are presented. FCI code has been used with a processing out of LTE of atomic physics of gold and of multigroup photonics. Emission and reabsorption of gold and aluminium lines are included.

  2. Ethical implications of excessive cluster sizes in cluster randomised trials.

    Science.gov (United States)

    Hemming, Karla; Taljaard, Monica; Forbes, Gordon; Eldridge, Sandra M; Weijer, Charles

    2018-02-20

    The cluster randomised trial (CRT) is commonly used in healthcare research. It is the gold-standard study design for evaluating healthcare policy interventions. A key characteristic of this design is that as more participants are included, in a fixed number of clusters, the increase in achievable power will level off. CRTs with cluster sizes that exceed the point of levelling-off will have excessive numbers of participants, even if they do not achieve nominal levels of power. Excessively large cluster sizes may have ethical implications due to exposing trial participants unnecessarily to the burdens of both participating in the trial and the potential risks of harm associated with the intervention. We explore these issues through the use of two case studies. Where data are routinely collected, available at minimum cost and the intervention poses low risk, the ethical implications of excessively large cluster sizes are likely to be low (case study 1). However, to maximise the social benefit of the study, identification of excessive cluster sizes can allow for prespecified and fully powered secondary analyses. In the second case study, while there is no burden through trial participation (because the outcome data are routinely collected and non-identifiable), the intervention might be considered to pose some indirect risk to patients and risks to the healthcare workers. In this case study it is therefore important that the inclusion of excessively large cluster sizes is justifiable on other grounds (perhaps to show sustainability). In any randomised controlled trial, including evaluations of health policy interventions, it is important to minimise the burdens and risks to participants. Funders, researchers and research ethics committees should be aware of the ethical issues of excessively large cluster sizes in cluster trials. © Article author(s) (or their employer(s) unless otherwise stated in the text of the article) 2018. All rights reserved. No commercial use is

  3. Gold Nanoparticle Microwave Synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Krantz, Kelsie E. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Christian, Jonathan H. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Coopersmith, Kaitlin [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Washington, II, Aaron L. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Murph, Simona H. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2016-07-27

    At the nanometer scale, numerous compounds display different properties than those found in bulk material that can prove useful in areas such as medicinal chemistry. Gold nanoparticles, for example, display promise in newly developed hyperthermia therapies for cancer treatment. Currently, gold nanoparticle synthesis is performed via the hot injection technique which has large variability in final particle size and a longer reaction time. One underdeveloped area by which these particles could be produced is through microwave synthesis. To initiate heating, microwaves agitate polar molecules creating a vibration that gives off the heat energy needed. Previous studies have used microwaves for gold nanoparticle synthesis; however, polar solvents were used that partially absorbed incident microwaves, leading to partial thermal heating of the sample rather than taking full advantage of the microwave to solely heat the gold nanoparticle precursors in a non-polar solution. Through this project, microwaves were utilized as the sole heat source, and non-polar solvents were used to explore the effects of microwave heating only as pertains to the precursor material. Our findings show that the use of non-polar solvents allows for more rapid heating as compared to polar solvents, and a reduction in reaction time from 10 minutes to 1 minute; this maximizes the efficiency of the reaction, and allows for reproducibility in the size/shape of the fabricated nanoparticles.

  4. Bioassisted Phytomining of Gold

    Science.gov (United States)

    Maluckov, Biljana S.

    2015-05-01

    Bioassisted phytomining implies targeted use of microorganisms and plants for the selective recovery of the metal. Metals from undissolved compounds are dissolved by applying specially chosen microorganisms and therefore become available to the hyperaccumulating plants. In the article, the selective extraction method of base metals and the precious metal gold by using microorganisms and plants is discussed.

  5. Digging for Gold

    Science.gov (United States)

    Waters, John K.

    2012-01-01

    In the case of higher education, the hills are more like mountains of data that "we're accumulating at a ferocious rate," according to Gerry McCartney, CIO of Purdue University (Indiana). "Every higher education institution has this data, but it just sits there like gold in the ground," complains McCartney. Big Data and the new tools people are…

  6. GOLD PRESSURE VESSEL SEAL

    Science.gov (United States)

    Smith, A.E.

    1963-11-26

    An improved seal between the piston and die member of a piston-cylinder type pressure vessel is presented. A layer of gold, of sufficient thickness to provide an interference fit between the piston and die member, is plated on the contacting surface of at least one of the members. (AEC)

  7. Gold Nanoparticle Microwave Synthesis

    International Nuclear Information System (INIS)

    Krantz, Kelsie E.; Christian, Jonathan H.; Coopersmith, Kaitlin; Washington II, Aaron L.; Murph, Simona H.

    2016-01-01

    At the nanometer scale, numerous compounds display different properties than those found in bulk material that can prove useful in areas such as medicinal chemistry. Gold nanoparticles, for example, display promise in newly developed hyperthermia therapies for cancer treatment. Currently, gold nanoparticle synthesis is performed via the hot injection technique which has large variability in final particle size and a longer reaction time. One underdeveloped area by which these particles could be produced is through microwave synthesis. To initiate heating, microwaves agitate polar molecules creating a vibration that gives off the heat energy needed. Previous studies have used microwaves for gold nanoparticle synthesis; however, polar solvents were used that partially absorbed incident microwaves, leading to partial thermal heating of the sample rather than taking full advantage of the microwave to solely heat the gold nanoparticle precursors in a non-polar solution. Through this project, microwaves were utilized as the sole heat source, and non-polar solvents were used to explore the effects of microwave heating only as pertains to the precursor material. Our findings show that the use of non-polar solvents allows for more rapid heating as compared to polar solvents, and a reduction in reaction time from 10 minutes to 1 minute; this maximizes the efficiency of the reaction, and allows for reproducibility in the size/shape of the fabricated nanoparticles.

  8. Preparation of gold microparticles using halide ions in bulk block copolymer phases via photoreduction

    International Nuclear Information System (INIS)

    Cha, Sang-Ho; Kim, Ki-Hyun; Lee, Won-Ki; Lee, Jong-Chan

    2009-01-01

    Gold microparticles were prepared from the gold salt in the solid bulk phase of a poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymer via a photoreduction process in the presence of halide ions. The shapes and sizes of the gold microparticles were found to be dependent on the types and amount of halide ions as well as the types of cations used due to the combined effects of the adsorption power and oxidative dissolution ability of the additives on gold surfaces. Gold nanorods were obtained when poly(ethylene oxide) was used instead of the block copolymer. This suggests that the poly(propylene oxide) (PPO) parts in the block copolymer are essential for the formation of gold microparticles, even though the degree of the direct interaction between the PPO blocks and gold salt is not significant. - Graphical abstract: Gold microparticles were successfully prepared using halide ions as additives in the polymeric bulk phase via photoreduction with the glow lamp irradiation.

  9. Disintegration of swift carbon clusters during passage through matter

    International Nuclear Information System (INIS)

    Koch, K.; Otteken, D.; Tuszynski, W.; Seidl, M.; Voit, H.

    2003-01-01

    Thin luminescent foils covered upstream with layers of Formvar or gold of various thicknesses were bombarded with C 8 clusters with energies between 5 and 10 MeV. The C 8 induced relative luminescence yield Φ 8 increases with growing layer thickness and approaches smoothly the value 8Φ 1 , i.e., the luminescence yield induced by eight well-separated C 1 cluster constituents. This is a clear demonstration of the gradual separation between the cluster constituents during the passage of the cluster through the layers. The layer thickness necessary to separate cluster constituents far enough to act as independent atomic ions with respect to the luminescence process was calculated. The result is that Formvar layers with a thickness of about 1150 nm or ≅250-nm-thick gold layers are necessary to establish this mutual independence of the cluster constituents. Both calculated values agree roughly with the layer thickness obtained from an extrapolation of the experimental data

  10. Gold and gold working in Late Bronze Age Northern Greece

    Science.gov (United States)

    Vavelidis, M.; Andreou, S.

    2008-04-01

    Numerous objects of gold displaying an impressive variety of types and manufacturing techniques are known from the Late Bronze Age (LBA) contexts of Mycenaean Greece, but very little is known about the origin and processing of gold during the second millennium b.c. Ancient literature and recent research indicate that northern Greece is probably the richest gold-bearing region in Greece, and yet, very little evidence exists regarding the exploitation of its deposits and the production as well as use of gold in the area during prehistory. The unusual find of a group of small stone crucibles at the prehistoric settlement of Thessaloniki Toumba, one with visible traces of gold melting, proves local production and offers a rare opportunity to examine the process of on-site gold working. Furthermore, the comparison of the chemical composition of prehistoric artefacts from two settlements with those of gold deposits in their immediate areas supports the local extraction of gold and opens up the prospect for some of the Mycenaean gold to have originated in northern Greece. The scarcity of gold items in northern Greek LBA contexts may not represent the actual amount of gold produced and consumed, but could be a result of the local social attitudes towards the circulation and deposition of artefacts from precious metals.

  11. Exploring backbone-cation alkyl spacers for multi-cation side chain anion exchange membranes

    Science.gov (United States)

    Zhu, Liang; Yu, Xuedi; Hickner, Michael A.

    2018-01-01

    In order to systematically study how the arrangement of cations on the side chain and length of alkyl spacers between cations impact the performance of multi-cation AEMs for alkaline fuel cells, a series of polyphenylene oxide (PPO)-based AEMs with different cationic side chains were synthesized. This work resulted in samples with two or three cations in a side chain pendant to the PPO backbone. More importantly, the length of the spacer between cations varied from 3 methylene (-CH2-) (C3) groups to 8 methylene (C8) groups. The highest conductivity, up to 99 mS/cm in liquid water at room temperature, was observed for the triple-cation side chain AEM with pentyl (C5) or hexyl (C6) spacers. The multi-cation AEMs were found to have decreased water uptake and ionic conductivity when the spacer chains between cations were lengthened from pentyl (C5) or hexyl (C6) to octyl (C8) linking groups. The triple-cation membranes with pentyl (C5) or hexyl (C6) groups between cations showed greatest stability after immersion in 1 M NaOH at 80 °C for 500 h.

  12. Identification of Paracoccidioides brasiliensis by gold nanoprobes

    Science.gov (United States)

    Martins, Jaciara F. S.; Castilho, Maiara L.; Cardoso, Maria A. G.; Carreiro, Andrea P.; Martin, Airton A.; Raniero, Leandro

    2012-01-01

    Paracoccidioides brasiliensis (P. brasiliensis) is a thermal dimorphic fungus and causal agent of paracoccidioidomycosis. Epidemiological data shows that it is mainly concentrated in Central and South America countries, with most registered cases in Colombia, Brazil, and Venezuela. The histopathological similarity with others fungal infection makes the diagnosis of P. brasiliensis more complicated. Therefore, the aim of this work was to find a positive and negative test for P. brasiliensis using gold nanoprobes as a new tool for P. brasiliensis detection. Gold nanoparticles were synthesized by reduction of gold chloride with sodium citrate. The results of this procedure is a wine-red solution with a maximum absorption in the range of ~520-530nm. A specific P. brasiliensis sequence of oligonucleotide was bonded to the nanoparticles, which maintained the wine-red color. The color changes from red to blue for negative diagnostic and is unchanged for a positive test. The H-bond interaction of DNA with the complementary DNA keeps strands together and forms double helical structure, maintaining the colloid stability. However, for non-complimentary DNA sequence the nanoprobes merge into a cluster, changing the light absorption.

  13. Clustering Dycom

    KAUST Repository

    Minku, Leandro L.

    2017-10-06

    Background: Software Effort Estimation (SEE) can be formulated as an online learning problem, where new projects are completed over time and may become available for training. In this scenario, a Cross-Company (CC) SEE approach called Dycom can drastically reduce the number of Within-Company (WC) projects needed for training, saving the high cost of collecting such training projects. However, Dycom relies on splitting CC projects into different subsets in order to create its CC models. Such splitting can have a significant impact on Dycom\\'s predictive performance. Aims: This paper investigates whether clustering methods can be used to help finding good CC splits for Dycom. Method: Dycom is extended to use clustering methods for creating the CC subsets. Three different clustering methods are investigated, namely Hierarchical Clustering, K-Means, and Expectation-Maximisation. Clustering Dycom is compared against the original Dycom with CC subsets of different sizes, based on four SEE databases. A baseline WC model is also included in the analysis. Results: Clustering Dycom with K-Means can potentially help to split the CC projects, managing to achieve similar or better predictive performance than Dycom. However, K-Means still requires the number of CC subsets to be pre-defined, and a poor choice can negatively affect predictive performance. EM enables Dycom to automatically set the number of CC subsets while still maintaining or improving predictive performance with respect to the baseline WC model. Clustering Dycom with Hierarchical Clustering did not offer significant advantage in terms of predictive performance. Conclusion: Clustering methods can be an effective way to automatically generate Dycom\\'s CC subsets.

  14. Clustering analysis

    International Nuclear Information System (INIS)

    Romli

    1997-01-01

    Cluster analysis is the name of group of multivariate techniques whose principal purpose is to distinguish similar entities from the characteristics they process.To study this analysis, there are several algorithms that can be used. Therefore, this topic focuses to discuss the algorithms, such as, similarity measures, and hierarchical clustering which includes single linkage, complete linkage and average linkage method. also, non-hierarchical clustering method, which is popular name K -mean method ' will be discussed. Finally, this paper will be described the advantages and disadvantages of every methods

  15. Cluster analysis

    CERN Document Server

    Everitt, Brian S; Leese, Morven; Stahl, Daniel

    2011-01-01

    Cluster analysis comprises a range of methods for classifying multivariate data into subgroups. By organizing multivariate data into such subgroups, clustering can help reveal the characteristics of any structure or patterns present. These techniques have proven useful in a wide range of areas such as medicine, psychology, market research and bioinformatics.This fifth edition of the highly successful Cluster Analysis includes coverage of the latest developments in the field and a new chapter dealing with finite mixture models for structured data.Real life examples are used throughout to demons

  16. Cluster editing

    DEFF Research Database (Denmark)

    Böcker, S.; Baumbach, Jan

    2013-01-01

    . The problem has been the inspiration for numerous algorithms in bioinformatics, aiming at clustering entities such as genes, proteins, phenotypes, or patients. In this paper, we review exact and heuristic methods that have been proposed for the Cluster Editing problem, and also applications......The Cluster Editing problem asks to transform a graph into a disjoint union of cliques using a minimum number of edge modifications. Although the problem has been proven NP-complete several times, it has nevertheless attracted much research both from the theoretical and the applied side...

  17. Innovative preparation of Au/C by replication of gold-containing mesoporous silica catalysts

    KAUST Repository

    Kerdi, Fatmé

    2010-01-01

    A new strategy, based on the nanocasting concept, has been used to prepare gold nanoparticles (NPs) highly dispersed in meso-structured carbons. Gold is first introduced in various functionalized mesostructured silicas (MCM-48 and SBA-15) and particles are formed inside the porosity upon reduction of Au 3+ cations. Silica pores are then impregnated with a carbon precursor and the composite material is heated at 900°C under vacuum. Silica is then removed by acid leaching, leading to partially encapsulated gold particles in mesoporous carbon. Carbon prevents aggregation of gold particles at high temperature, both the mean size and distribution being similar to those observed in silica. However, while Au@SiO2 exhibit significant catalytic activity in the aerobic oxidation of trans-stilbene in the liquid phase, its Au@C mesostructured replica is quite inactive. © 2010 Elsevier B.V. All rights reserved.

  18. Cation transport in isomeric pentanes

    International Nuclear Information System (INIS)

    Gyoergy, Istvan; Gee, Norman; Freeman, G.R.

    1985-01-01

    The cation mobility μsub(+) is measured in n-pentane, isopentane, neo-pentane, and mixtures of n- and neo-pentane over conditions from the normal liquid, through the critical fluid, to the low density gas. Most of the liquid data correlate with the reduced temperature T/Tsub(c). The T/Tsub(c) reflects free volume and viscosity changes. Comparison is made to neutral molecule diffusion. The transition from viscosity control of mobility in the liquid to density control in the dilute gas occurs over the reduced viscosity region 3 > eta/etasub(c) > 0.6, which corresponds to the reduced density region 1.9 > eta/etasub(c) > 0.5. In the saturated gas etaμsub(+) is similar in all pentanes, but iso- approximately> n- > neo-pentane. At constant density dμsub(+)/dT >= 0 for gases. The average gas nμsub(+) is similar in all pentanes, but iso- approximately> n- > neo-pentane. At constant density dμsub(+)/dT >= 0 for gases. The average momentum transfer cross sections in the n-/neo-pentane mixtures are similar to those in neo-pentane at low T but similar to those in n-pentane at high T. The present findings are combined with previous electron mobility data in addressing the effect of hydrocarbon molecular (external) shape on the electric breakdown strength of gases

  19. Cationic Bolaamphiphiles for Gene Delivery

    Science.gov (United States)

    Tan, Amelia Li Min; Lim, Alisa Xue Ling; Zhu, Yiting; Yang, Yi Yan; Khan, Majad

    2014-05-01

    Advances in medical research have shed light on the genetic cause of many human diseases. Gene therapy is a promising approach which can be used to deliver therapeutic genes to treat genetic diseases at its most fundamental level. In general, nonviral vectors are preferred due to reduced risk of immune response, but they are also commonly associated with low transfection efficiency and high cytotoxicity. In contrast to viral vectors, nonviral vectors do not have a natural mechanism to overcome extra- and intracellular barriers when delivering the therapeutic gene into cell. Hence, its design has been increasingly complex to meet challenges faced in targeting of, penetration of and expression in a specific host cell in achieving more satisfactory transfection efficiency. Flexibility in design of the vector is desirable, to enable a careful and controlled manipulation of its properties and functions. This can be met by the use of bolaamphiphile, a special class of lipid. Unlike conventional lipids, bolaamphiphiles can form asymmetric complexes with the therapeutic gene. The advantage of having an asymmetric complex lies in the different purposes served by the interior and exterior of the complex. More effective gene encapsulation within the interior of the complex can be achieved without triggering greater aggregation of serum proteins with the exterior, potentially overcoming one of the great hurdles faced by conventional single-head cationic lipids. In this review, we will look into the physiochemical considerations as well as the biological aspects of a bolaamphiphile-based gene delivery system.

  20. Moessbauerspectroscopy on Gold Ruby Glass

    International Nuclear Information System (INIS)

    Haslbeck, S.

    2005-01-01

    In this thesis, the chemical states of gold and the physical mechanisms of the growing process of the particles under the influence of additional ingredients like tin, lead, antimony and selenium before, during and after the colouring process are investigated by using the Moessbauer spectroscopy on 197 Au, 119 Sn and 121 Sb, optical spectroscopy and X-ray-diffraction. Gold in an unnealed, colourless state of the glasses consists of monovalent forming linear bonds to two neighbouring oxygen atoms. The Lamb-Moessbauer factor of these gold oxide bondings is observed as 0.095 at 4.2 K. The gold in it's oxide state transforms to gold particles with a diameter of 3 nm to 60 nm. The size of the gold particles is quite definable within the optical spectra and certain sizes are also discernable within the Moessbauer spectra. One component of the Moessbauer spectra is assigned to the surface layer of the gold particles. By comparing this surface component with the amount of the bulk metallic core, one can calculate the size of the gold particles. In the Moessbauer spectra of the colourless glass one also can find parts of bulk metallic gold. Investigations with X-ray diffraction show that these are gold particles with a diameter of 100 nm to 300 nm and therefore have no additional colouring effect within the visible spectrum. The Moessbauer spectra on gold of the remelt glasses are similar to those which have been measured on the initial colourless glasses

  1. Conductometric gas sensors based on metal oxides modified with gold nanoparticles: a review

    International Nuclear Information System (INIS)

    Korotcenkov, Ghenadii; Cho, Beong K.; Brinzari, Vladimir

    2016-01-01

    This review (with 170 refs.) discusses approaches towards surface functionalizaton of metal oxides by gold nanoparticles, and the application of the resulting nanomaterials in resistive gas sensors. The articles is subdivided into sections on (a) methods for modification of metal oxides with gold nanoparticles; (b) the response of gold nanoparticle-modified metal oxide sensors to gaseous species, (c) a discussion of the limitations of such sensors, and (d) a discussion on future tasks and trends along with an outlook. It is shown that, in order to achieve significant improvements in sensor parameters, it is necessary to warrant a good control the size and density of gold nanoparticles on the surface of metal oxide crystallites, the state of gold in the cluster, and the properties of the metal oxide support. Current challenges include an improved reproducibility of sensor preparation, better long-term stabilities, and a better resistance to sintering and poisoning of gold clusters during operation. Additional research focused on better understanding the role of gold clusters and nanoparticles in gas-sensing effects is also required. (author)

  2. For the love of gold

    International Nuclear Information System (INIS)

    Young, J.E.

    1993-01-01

    Gold is found in minute quantities and gold mining generates enormous amounts of waste materials and long history of environmental destruction: mercury in tailing, eroded land, and acid mine drainage are legacies of the past. The problem has become worse in recent years in North America, Australia, the Amazon basin, Philippines. This paper describes the economics of gold and the changes in the world economy which has precipitated the new gold rushes. Current technology uses a cyanide solution for leaching small amounts of gold from tons of waste, and mercury remains a toxic waste of gold mining. Both short and long term results of gold mining, on the environment and on indiginous populations are described

  3. Stressor states and the cation crossroads.

    Science.gov (United States)

    Weber, Karl T; Bhattacharya, Syamal K; Newman, Kevin P; Soberman, Judith E; Ramanathan, Kodangudi B; McGee, Jesse E; Malik, Kafait U; Hickerson, William L

    2010-12-01

    Neurohormonal activation involving the hypothalamic-pituitary-adrenal axis and adrenergic nervous and renin-angiotensin-aldosterone systems is integral to stressor state-mediated homeostatic responses. The levels of effector hormones, depending upon the degree of stress, orchestrate the concordant appearance of hypokalemia, ionized hypocalcemia and hypomagnesemia, hypozincemia, and hyposelenemia. Seemingly contradictory to homeostatic responses wherein the constancy of extracellular fluid would be preserved, upregulation of cognate-binding proteins promotes coordinated translocation of cations to injured tissues, where they participate in wound healing. Associated catecholamine-mediated intracellular cation shifts regulate the equilibrium between pro-oxidants and antioxidant defenses, a critical determinant of cell survival. These acute and chronic stressor-induced iterations in extracellular and intracellular cations are collectively referred to as the cation crossroads. Intracellular cation shifts, particularly excessive accumulation of Ca2+, converge on mitochondria to induce oxidative stress and raise the opening potential of their inner membrane permeability transition pores (mPTPs). The ensuing loss of cationic homeostasis and adenosine triphosphate (ATP) production, together with osmotic swelling, leads to organellar degeneration and cellular necrosis. The overall impact of iterations in extracellular and intracellular cations and their influence on cardiac redox state, cardiomyocyte survival, and myocardial structure and function are addressed herein.

  4. Kinetic Assembly of Near-IR Active Gold Nanoclusters using Weakly Adsorbing Polymers to Control Size

    Science.gov (United States)

    Tam, Jasmine M.; Murthy, Avinash K.; Ingram, Davis R.; Nguyen, Robin; Sokolov, Konstantin V.; Johnston, Keith P.

    2013-01-01

    Clusters of metal nanoparticles with an overall size less than 100 nm and high metal loadings for strong optical functionality, are of interest in various fields including microelectronics, sensors, optoelectronics and biomedical imaging and therapeutics. Herein we assemble ~5 nm gold particles into clusters with controlled size, as small as 30 nm and up to 100 nm, which contain only small amounts of polymeric stabilizers. The assembly is kinetically controlled with weakly adsorbing polymers, PLA(2K)-b-PEG(10K)-b-PLA(2K) or PEG (MW = 3350), by manipulating electrostatic, van der Waals (VDW), steric, and depletion forces. The cluster size and optical properties are tuned as a function of particle volume fractions and polymer/gold ratios to modulate the interparticle interactions. The close spacing between the constituent gold nanoparticles and high gold loadings (80–85% w/w gold) produce a strong absorbance cross section of ~9×10−15 m2 in the NIR at 700 nm. This morphology results from VDW and depletion attractive interactions that exclude the weakly adsorbed polymeric stabilizer from the cluster interior. The generality of this kinetic assembly platform is demonstrated for gold nanoparticles with a range of surface charges from highly negative to neutral, with the two different polymers. PMID:20361735

  5. DNA-mediated self-assembly of tetrahedral plasmonic clusters for metafluids

    Science.gov (United States)

    Schade, Nicholas; Sun, Li; Lee, You-Jin; Fan, Jonathan; Capasso, Federico; Yi, Gi-Ra; Manoharan, Vinothan

    2014-03-01

    We direct the self-assembly of clusters of gold nanospheres with the goal of creating a bulk, isotropic, optical metafluid. We use spherical gold nanoparticles that are exceptionally smooth, monocrystalline, and monodisperse. These particles exhibit highly reproducible scattering spectra compared with commercially available gold colloids. We label them with DNA sequences and mix them together to self-assemble small clusters. By controlling the particle sizes and the interactions between them, we maximize the yield of tetrahedral clusters, the ideal structures for isotropic metamaterials.

  6. Occupational Clusters.

    Science.gov (United States)

    Pottawattamie County School System, Council Bluffs, IA.

    The 15 occupational clusters (transportation, fine arts and humanities, communications and media, personal service occupations, construction, hospitality and recreation, health occupations, marine science occupations, consumer and homemaking-related occupations, agribusiness and natural resources, environment, public service, business and office…

  7. Fuzzy Clustering

    DEFF Research Database (Denmark)

    Berks, G.; Keyserlingk, Diedrich Graf von; Jantzen, Jan

    2000-01-01

    A symptom is a condition indicating the presence of a disease, especially, when regarded as an aid in diagnosis.Symptoms are the smallest units indicating the existence of a disease. A syndrome on the other hand is an aggregate, set or cluster of concurrent symptoms which together indicate...... and clustering are the basic concerns in medicine. Classification depends on definitions of the classes and their required degree of participant of the elements in the cases' symptoms. In medicine imprecise conditions are the rule and therefore fuzzy methods are much more suitable than crisp ones. Fuzzy c......-mean clustering is an easy and well improved tool, which has been applied in many medical fields. We used c-mean fuzzy clustering after feature extraction from an aphasia database. Factor analysis was applied on a correlation matrix of 26 symptoms of language disorders and led to five factors. The factors...

  8. First-Principles Modeling of ThO2 Solid Solutions with Oxides of Trivalent Cations

    Science.gov (United States)

    Alexandrov, Vitaly; Asta, Mark; Gronbech-Jensen, Niels

    2010-03-01

    Solid solutions formed by doping ThO2 with oxides of trivalent cations, such as Y2O3 and La2O3, are suitable for solid electrolyte applications, similar to doped zirconia and ceria. ThO2 has also been gaining much attention as an alternative to UO2 in nuclear energy applications, the aforementioned trivalent cations being important fission products. In both cases the mixing energetics and short-range ordering/clustering are key to understanding structural and transport properties. Using first-principles atomistic calculations, we address intra- and intersublattice interactions for both cation and anion sublattices in ThO2-based fluorite-type solid solutions and compare the results with similar modeling studies for related trivalent-doped zirconia systems.

  9. Cation distributions on rapidly solidified cobalt ferrite

    Science.gov (United States)

    De Guire, Mark R.; Kalonji, Gretchen; O'Handley, Robert C.

    1990-01-01

    The cation distributions in two rapidly solidified cobalt ferrites have been determined using Moessbauer spectroscopy at 4.2 K in an 8-T magnetic field. The samples were obtained by gas atomization of a Co0-Fe2O3-P2O5 melt. The degree of cation disorder in both cases was greater than is obtainable by cooling unmelted cobalt ferrite. The more rapidly cooled sample exhibited a smaller departure from the equilibrium cation distribution than did the more slowly cooled sample. This result is explained on the basis of two competing effects of rapid solidification: high cooling rate of the solid, and large undercooling.

  10. Radioimmunoassay of human eosinophil cationic protein

    International Nuclear Information System (INIS)

    Venge, P.; Roxin, L.E.; Olsson, I.

    1977-01-01

    A radioimmunosorbent assay has been developed which allows the detection in serum of a cationic protein derived from eosinophil granulocytes. In 34 healthy individuals the mean level was 31 μg/l. with a range of 5 to 55 μg/l. The serum concentration of 'eosinophil' cationic protein was correlated (P<0.001) to the number of eosinophil granulocytes in peripheral blood. Quantitiation of 'eosinophil' cationic protein in serum might be useful in the study of eosinophil granulocyte turnover and function in vivo. (author)

  11. Cluster generator

    Science.gov (United States)

    Donchev, Todor I [Urbana, IL; Petrov, Ivan G [Champaign, IL

    2011-05-31

    Described herein is an apparatus and a method for producing atom clusters based on a gas discharge within a hollow cathode. The hollow cathode includes one or more walls. The one or more walls define a sputtering chamber within the hollow cathode and include a material to be sputtered. A hollow anode is positioned at an end of the sputtering chamber, and atom clusters are formed when a gas discharge is generated between the hollow anode and the hollow cathode.

  12. Cluster Bulleticity

    OpenAIRE

    Massey, Richard; Kitching, Thomas; Nagai, Daisuke

    2010-01-01

    The unique properties of dark matter are revealed during collisions between clusters of galaxies, such as the bullet cluster (1E 0657−56) and baby bullet (MACS J0025−12). These systems provide evidence for an additional, invisible mass in the separation between the distributions of their total mass, measured via gravitational lensing, and their ordinary ‘baryonic’ matter, measured via its X-ray emission. Unfortunately, the information available from these systems is limited by their rarity. C...

  13. Cluster headache

    OpenAIRE

    Leroux, Elizabeth; Ducros, Anne

    2008-01-01

    Abstract Cluster headache (CH) is a primary headache disease characterized by recurrent short-lasting attacks (15 to 180 minutes) of excruciating unilateral periorbital pain accompanied by ipsilateral autonomic signs (lacrimation, nasal congestion, ptosis, miosis, lid edema, redness of the eye). It affects young adults, predominantly males. Prevalence is estimated at 0.5–1.0/1,000. CH has a circannual and circadian periodicity, attacks being clustered (hence the name) in bouts that can occur ...

  14. A series of intrinsically chiral gold nanocage structures.

    Science.gov (United States)

    Liu, X J; Hamilton, I P

    2017-07-27

    We present a series of intrinsically chiral gold nanocage structures, Au 9n+6 , which are stable for n ≥ 2. These structures consist of an Au 9n tube which is capped with Au 3 units at each end. Removing the Au 3 caps, we obtain a series of intrinsically chiral gold nanotube structures, Au 9n , which are stable for n ≥ 4. The intrinsic chirality of these structures results from the helicity of the gold strands which form the tube and not because an individual Au atom is a chiral center. The symmetry of these structures is C 3 and substructures of gold hexagons with a gold atom in the middle are particularly prominent. We focus on the properties of Au 42 (C 3 ) and Au 105 (C 3 ) which are the two smallest gold nanocage structures to be completely tiled by these Au 7 "golden-eye" substructures. Our main focus is on Au 42 (C 3 ) since gold clusters in the 40-50 atom regime are currently being investigated in gas phase experiments. We show that the intrinsically chiral Au 42 cage structure is energetically comparable with previously reported achiral cage and compact Au 42 structures. Cage structures are of particular interest because species can be encapsulated (and stabilized) inside the cage and we provide strong evidence that Au 6 @Au 42 (C 3 ) is the global minimum Au 48 structure. The intrinsically chiral gold nanocage structures, which exhibit a range of size-related properties, have potential applications in chiral catalysis and as components in nanostructured devices.

  15. Rushing for gold

    DEFF Research Database (Denmark)

    Jønsson, Jesper Bosse; Bryceson, Deborah Fahy

    2009-01-01

    African rural dwellers have faced depressed economic prospects for several decades. Now, in a number of mineral-rich countries, multiple discoveries of gold and precious stones have attracted large numbers of prospective small-scale miners. While their 'rush' to, and activities within, mining sit...... affluent than the others, suggesting that movement can be rewarding for those willing to 'try their luck' with the hard work and social networking demands of mining another site.......African rural dwellers have faced depressed economic prospects for several decades. Now, in a number of mineral-rich countries, multiple discoveries of gold and precious stones have attracted large numbers of prospective small-scale miners. While their 'rush' to, and activities within, mining sites...

  16. Gold' 82 - technical sessions

    International Nuclear Information System (INIS)

    Viewing, K.

    1983-01-01

    Sulphur-isotope studies had been applied by Dr. I. Lambert to a number of deposits in Western Australia and also to certain samples from Vubachickwe and other deposits in Zimbabwe. A study of the sulphur isotopes at the Dickenson Mine, revealed a wide spread of values in the mineralised zones. Metamorphic processes were likely to be significant in the concentration of gold. The iron formations at the Old Jardine Mine had been unfolded by Dr. W.S. Hallager and the pattern of sedimentation was unraveled. A gold-rich zone was separated by a barren gap from the other part of the mineralised zone. Research was also done on the effects of the metamorphic processes, and the ages of mineralisation

  17. Radioactive gold ring dermatitis

    International Nuclear Information System (INIS)

    Miller, R.A.; Aldrich, J.E.

    1990-01-01

    A superficial squamous cell carcinoma developed in a woman who wore a radioactive gold ring for more than 30 years. Only part of the ring was radioactive. Radiation dose measurements indicated that the dose to basal skin layer was 2.4 Gy (240 rad) per week. If it is assumed that the woman continually wore her wedding ring for 37 years since purchase, she would have received a maximum dose of approximately 4600 Gy

  18. Glucose oxidase-functionalized fluorescent gold nanoclusters as probes for glucose

    International Nuclear Information System (INIS)

    Xia, Xiaodong; Long, Yunfei; Wang, Jianxiu

    2013-01-01

    Highlights: ► A glucose oxidase/gold nanocluster conjugates formed by etching chemistry. ► Integration of the bioactivities and fluorescence properties within a single unit. ► These conjugates serve as novel fluorescent probe for glucose. -- Abstract: Creation and application of noble metal nanoclusters have received continuous attention. By integrating enzyme activity and fluorescence for potential applications, enzyme-capped metal clusters are more desirable. This work demonstrated a glucose oxidase (an enzyme for glucose)-functionalized gold cluster as probe for glucose. Under physiological conditions, such bioconjugate was successfully prepared by an etching reaction, where tetrakis (hydroxylmethyl) phosphonium-protected gold nanoparticle and thioctic acid-modified glucose oxidase were used as precursor and etchant, respectively. These bioconjugates showed unique fluorescence spectra (λ em max = 650 nm, λ ex max = 507 nm) with an acceptable quantum yield (ca. 7%). Moreover, the conjugated glucose oxidase remained active and catalyzed reaction of glucose and dissolved O 2 to produce H 2 O 2 , which quenched quantitatively the fluorescence of gold clusters and laid a foundation of glucose detection. A linear range of 2.0 × 10 −6 –140 × 10 −6 M and a detection limit of 0.7 × 10 −6 M (S/N = 3) were obtained. Also, another horseradish peroxidase/gold cluster bioconjugate was produced by such general synthesis method. Such enzyme/metal cluster bioconjugates represented a promising class of biosensors for biologically important targets in organelles or cells

  19. Cationization of heparin for film applications

    Czech Academy of Sciences Publication Activity Database

    Šimkovic, I.; Mendichi, R.; Kelnar, Ivan; Filip, J.; Hricovíni, M.

    2015-01-01

    Roč. 115, 22 January (2015), s. 551-558 ISSN 0144-8617 Institutional support: RVO:61389013 Keywords : heparin * cationization * NMR Subject RIV: CD - Macromolecular Chemistry Impact factor: 4.219, year: 2015

  20. Functionalization of lamellar molybdenum disulphide nanocomposite with gold nanoparticles

    International Nuclear Information System (INIS)

    Lavayen, V.; O'Dwyer, C.; Ana, M.A. Santa; Mirabal, N.; Benavente, E.; Cardenas, G.; Gonzalez, G.; Torres, C.M. Sotomayor

    2007-01-01

    This work explores the functionalization of an organic-inorganic MoS 2 lamellar compound, prepared by a chemical liquid deposition method (CLD), that has an interlamellar distance of ∼5.2 nm, using clusters of gold nanoparticles. The gold nanoparticles have a mean diameter of 1.2 nm, a stability of ∼85 days, and a zeta potential measured to be ζ -6.8 mV (solid). The nanoparticles are localized in the hydrophilic zones, defined by the presence of amine groups of the surfactant between the lamella of MoS 2 . SEM, TEM, EDAX and electron diffraction provide conclusive evidence of the interlamellar insertion of the gold nanoparticles in the MoS 2

  1. Functionalization of lamellar molybdenum disulphide nanocomposite with gold nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Lavayen, V. [Tyndall National Institute, University College Cork, Lee Maltings, Prospect Row, Cork (Ireland) and Department of Chemistry, Faculty of Sciences, Universidad de Chile, P.O. Box 653, Santiago (Chile)]. E-mail: vlavayen@tyndall.ie; O' Dwyer, C. [Tyndall National Institute, University College Cork, Lee Maltings, Prospect Row, Cork (Ireland); Ana, M.A. Santa [Department of Chemistry, Faculty of Sciences, Universidad de Chile, P.O. Box 653, Santiago (Chile); Mirabal, N. [Department of Chemistry, Faculty of Sciences, Universidad de Chile, P.O. Box 653, Santiago (Chile); Benavente, E. [Department of Chemistry, Universidad Tecnologica Metropolitana, P.O. Box 9845, Santiago (Chile); Cardenas, G. [Department of Polymers, Faculty of Chemistry Science, Universidad de Concepcion, P.O. Box 160-C, Concepcion (Chile); Gonzalez, G. [Department of Chemistry, Faculty of Sciences, Universidad de Chile, P.O. Box 653, Santiago (Chile); Torres, C.M. Sotomayor [Tyndall National Institute, University College Cork, Lee Maltings, Prospect Row, Cork (Ireland)

    2007-01-30

    This work explores the functionalization of an organic-inorganic MoS{sub 2} lamellar compound, prepared by a chemical liquid deposition method (CLD), that has an interlamellar distance of {approx}5.2 nm, using clusters of gold nanoparticles. The gold nanoparticles have a mean diameter of 1.2 nm, a stability of {approx}85 days, and a zeta potential measured to be {zeta} -6.8 mV (solid). The nanoparticles are localized in the hydrophilic zones, defined by the presence of amine groups of the surfactant between the lamella of MoS{sub 2}. SEM, TEM, EDAX and electron diffraction provide conclusive evidence of the interlamellar insertion of the gold nanoparticles in the MoS{sub 2}.

  2. The expanding universe of thiolated gold nanoclusters and beyond.

    Science.gov (United States)

    Jiang, De-en

    2013-08-21

    Thiolated gold nanoclusters form a universe of their own. Researchers in this field are constantly pushing the boundary of this universe by identifying new compositions and in a few "lucky" cases, solving their structures. Such solved structures, even if there are only few, provide important hints for predicting the many identified compositions that are yet to be crystallized or structure determined. Structure prediction is the most pressing issue for a computational chemist in this field. The success of the density functional theory method in gauging the energetic ordering of isomers for thiolated gold clusters has been truly remarkable, but to predict the most stable structure for a given composition remains a great challenge. In this feature article from a computational chemist's point of view, the author shows how one understands and predicts structures for thiolated gold nanoclusters based on his old and new results. To further entertain the reader, the author also offers several "imaginative" structures, claims, and challenges for this field.

  3. Test procedure for cation exchange chromatography

    International Nuclear Information System (INIS)

    Cooper, T.D.

    1994-01-01

    The purpose of this test plan is to demonstrate the synthesis of inorganic antimonate ion exchangers and compare their performance against the standard organic cation exchangers. Of particular interest is the degradation rate of both inorganic and organic cation exchangers. This degradation rate will be tracked by determining the ion exchange capacity and thermal stability as a function of time, radiation dose, and chemical reaction

  4. Cycloaliphatic epoxide resins for cationic UV - cure

    International Nuclear Information System (INIS)

    Verschueren, K.; Balwant Kaur

    1999-01-01

    This paper introduces the cyclo - aliphatic epoxide resins used for the various applications of radiation curing and their comparison with acrylate chemistry. Radiation curable coatings and inks are pre - dominantly based on acrylate chemistry but over the last few years, cationic chemistry has emerged successfully with the unique properties inherent with cyclo - aliphatic epoxide ring structures. Wide variety of cationic resins and diluents, the formulation techniques to achieve the desired properties greatly contributes to the advancement of UV - curing technology

  5. Chemical reactivity of cation-exchanged zeolites

    OpenAIRE

    Pidko, E.A.

    2008-01-01

    Zeolites modified with metal cations have been extensively studied during the last two decades because of their wide application in different technologically important fields such as catalysis, adsorption and gas separation. Contrary to the well-understood mechanisms of chemical reactions catalyzed by Brønsted acid sites in the hydrogen forms of zeolites, the nature of chemical reactivity, and related, the structure of the metal-containing ions in cation-exchanged zeolites remains the subject...

  6. Restructuring of a peat in interaction with multivalent cations: effect of cation type and aging time.

    Science.gov (United States)

    Kunhi Mouvenchery, Yamuna; Jaeger, Alexander; Aquino, Adelia J A; Tunega, Daniel; Diehl, Dörte; Bertmer, Marko; Schaumann, Gabriele Ellen

    2013-01-01

    It is assumed to be common knowledge that multivalent cations cross-link soil organic matter (SOM) molecules via cation bridges (CaB). The concept has not been explicitly demonstrated in solid SOM by targeted experiments, yet. Therefore, the requirements for and characteristics of CaB remain unidentified. In this study, a combined experimental and molecular modeling approach was adopted to investigate the interaction of cations on a peat OM from physicochemical perspective. Before treatment with salt solutions of Al(3+), Ca(2+) or Na(+), respectively, the original exchangeable cations were removed using cation exchange resin. Cation treatment was conducted at two different values of pH prior to adjusting pH to 4.1. Cation sorption is slower (>2 h) than deprotonation of functional groups (cation addition and decreased with increasing cation valency. Sorption coefficients were similar for all cations and at both pH. This contradicts the general expectations for electrostatic interactions, suggesting that not only the interaction chemistry but also spatial distribution of functional groups in OM determines binding of cations in this peat. The reaction of contact angle, matrix rigidity due to water molecule bridges (WaMB) and molecular mobility of water (NMR analysis) suggested that cross-linking via CaB has low relevance in this peat. This unexpected finding is probably due to the low cation exchange capacity, resulting in low abundance of charged functionalities. Molecular modeling demonstrates that large average distances between functionalities (∼3 nm in this peat) cannot be bridged by CaB-WaMB associations. However, aging strongly increased matrix rigidity, suggesting successive increase of WaMB size to connect functionalities and thus increasing degree of cross-linking by CaB-WaMB associations. Results thus demonstrated that the physicochemical structure of OM is decisive for CaB and aging-induced structural reorganisation can enhance cross-link formation.

  7. Formation of radical cations of diaryloxadiazoles

    International Nuclear Information System (INIS)

    Helmstreit, W.

    1988-01-01

    The nature of the formation of the radical cation of the 2,5-bis-(p-diethylaminophenyl)-1,3,4-oxadiazole (PC) in liquid n-butyl chloride and acetonitrile has been investigated by observing excited state fluorescence and transient absorption using nanosecond pulse radiolysis and laser flash photolysis. The formation of solute oxonium ions has also been observed. At concentrations -4 mol dm -3 the growth time at which the transient absorption of the radical cation reaches the maximum follows the rise time of the electron pulse ( 2 laser yields the solute radical cation in an acetonitrile solution of 2 x 10 -4 mol dm -3 PC via an electronically excited state. Here, the generation time was smaller than 5 ns. The yield of the cation is increased by addition of CCl 4 . A reaction mechanism is proposed that explains the fast cation formation in terms of an exciplex formed by interaction between an electronically excited state of diaryloxadiazole and the ground state of the solvent. This exciplex yields the solute radical cation. (author)

  8. Luminescent sulfides of monovalent and trivalent cations

    International Nuclear Information System (INIS)

    1975-01-01

    The invention discloses a family of luminescent materials or phosphors having a rhombohedral crystal structure and consisting essentially of a mixed host sulfide of at least one monovalent host cation and at least one trivalent host cation, and containing, for each mole of phosphor, 0.0005 to 0.05 mole of at least one activating cation. The monovalent host cations may be Na, K or Rb and Cs. The trivalent host cations may be Gd, La, Lu, Sc and Y. The activating cations may be one or more of trivalent As, Bi, Ce, Dy, Er, Pr, Sb, Sm, Tb and Tm; divalent Lu, Mn, Pb and Sn; and monovalent Ag, Cu and Tl. The novel phosphors may be used in devices to convert electron-beam, ultraviolet or x-ray energy to light in the visible spectrum. Such energy conversion can be employed for example in fluoroscopic screens, and in viewing screens of cathode-ray tubes and other electron tubes

  9. Geminate electron--cation recombination in disordered solids

    International Nuclear Information System (INIS)

    Berlin, Y.A.; Chekunaev, N.I.; Goldanskii, V.I.

    1990-01-01

    A theory of a geminate electron--cation recombination has been developed using the percolation approach to the description of the electron transport in disordered solids. Following this approach all trapping sites are separated into two groups. The first group forms a diffusion cluster responsible for the macroscopic charge transfer in disordered media whilethe second group consists of isolated traps playing the role of origins and sinks for mobile electrons. In the framework of such a model an equation has been derived describing the electron motion in the Coulomb field of a parent cation. The solution of this equation in the long time limit shows that the recombination rate decreases vs time as t -(1+α/2) with α being a positive constant or a very weak function of t. In the particular case of Gaussian diffusion α=1 and the kinetic law obtained reduces to that predicted by the well-known Onsager--Smoluchowski theory. However for the dispersive (non-Gaussian) transport in highly disordered systems α<1 and its value depends on the type of disorder, on the energy level structure of trapped electrons and on the specific mechanism of electron migration through the medium

  10. Organic non-aqueous cation-based redox flow batteries

    Science.gov (United States)

    Zhang, Lu; Huang, Jinhua; Burrell, Anthony

    2018-05-08

    The present invention provides a non-aqueous redox flow battery comprising a negative electrode immersed in a non-aqueous liquid negative electrolyte, a positive electrode immersed in a non-aqueous liquid positive electrolyte, and a cation-permeable separator (e.g., a porous membrane, film, sheet, or panel) between the negative electrolyte from the positive electrolyte. During charging and discharging, the electrolytes are circulated over their respective electrodes. The electrolytes each comprise an electrolyte salt (e.g., a lithium or sodium salt), a transition-metal free redox reactant, and optionally an electrochemically stable organic solvent. Each redox reactant is selected from an organic compound comprising a conjugated unsaturated moiety, a boron cluster compound, and a combination thereof. The organic redox reactant of the positive electrolyte comprises a tetrafluorohydroquinone ether compound or a tetrafluorocatechol ether compound.

  11. Organic non-aqueous cation-based redox flow batteries

    Science.gov (United States)

    Jansen, Andrew N.; Vaughey, John T.; Chen, Zonghai; Zhang, Lu; Brushett, Fikile R.

    2016-03-29

    The present invention provides a non-aqueous redox flow battery comprising a negative electrode immersed in a non-aqueous liquid negative electrolyte, a positive electrode immersed in a non-aqueous liquid positive electrolyte, and a cation-permeable separator (e.g., a porous membrane, film, sheet, or panel) between the negative electrolyte from the positive electrolyte. During charging and discharging, the electrolytes are circulated over their respective electrodes. The electrolytes each comprise an electrolyte salt (e.g., a lithium or sodium salt), a transition-metal free redox reactant, and optionally an electrochemically stable organic solvent. Each redox reactant is selected from an organic compound comprising a conjugated unsaturated moiety, a boron cluster compound, and a combination thereof. The organic redox reactant of the positive electrolyte is selected to have a higher redox potential than the redox reactant of the negative electrolyte.

  12. Divalent cation shrinks DNA but inhibits its compaction with trivalent cation.

    Science.gov (United States)

    Tongu, Chika; Kenmotsu, Takahiro; Yoshikawa, Yuko; Zinchenko, Anatoly; Chen, Ning; Yoshikawa, Kenichi

    2016-05-28

    Our observation reveals the effects of divalent and trivalent cations on the higher-order structure of giant DNA (T4 DNA 166 kbp) by fluorescence microscopy. It was found that divalent cations, Mg(2+) and Ca(2+), inhibit DNA compaction induced by a trivalent cation, spermidine (SPD(3+)). On the other hand, in the absence of SPD(3+), divalent cations cause the shrinkage of DNA. As the control experiment, we have confirmed the minimum effect of monovalent cation, Na(+) on the DNA higher-order structure. We interpret the competition between 2+ and 3+ cations in terms of the change in the translational entropy of the counterions. For the compaction with SPD(3+), we consider the increase in translational entropy due to the ion-exchange of the intrinsic monovalent cations condensing on a highly charged polyelectrolyte, double-stranded DNA, by the 3+ cations. In contrast, the presence of 2+ cation decreases the gain of entropy contribution by the ion-exchange between monovalent and 3+ ions.

  13. Dilution thermodynamics of the biologically relevant cation mixtures

    International Nuclear Information System (INIS)

    Kaczyński, Marek; Borowik, Tomasz; Przybyło, Magda; Langner, Marek

    2014-01-01

    Graphical abstract: - Highlights: • Dilution energetics of Ca 2+ can be altered by the aqueous phase ionic composition. • Dissipated heat upon Ca 2+ dilution is drastically reduced in the K + presence. • Reduction of the enthalpy change upon Ca 2+ dilution is K + concentration dependent. • The cooperativity of Ca 2+ hydration might be of great biological relevance providing a thermodynamic argument for the specific ionic composition of the intracellular environment. - Abstract: The ionic composition of intracellular space is rigorously controlled by a variety of processes consuming large quantities of energy. Since the energetic efficiency is an important evolutional criterion, therefore the ion fluxes within the cell should be optimized with respect to the accompanying energy consumption. In the paper we present the experimental evidence that the dilution enthalpies of the biologically relevant ions; i.e. calcium and magnesium depend on the presence of monovalent cations; i.e. sodium and potassium. The heat flow generated during the dilution of ionic mixtures was measured with the isothermal titration calorimetry. When calcium was diluted together with potassium the dilution enthalpy was drastically reduced as the function of the potassium concentration present in the solution. No such effect was observed when the potassium ions were substituted with sodium ones. When the dilution of magnesium was investigated the dependence of the dilution enthalpy on the accompanying monovalent cation was much weaker. In order to interpret experimental evidences the ionic cluster formation is postulated. The specific organization of such cluster should depend on ions charges, sizes and organization of the hydration layers

  14. Immunological properties of gold nanoparticles.

    Science.gov (United States)

    Dykman, Lev A; Khlebtsov, Nikolai G

    2017-03-01

    In the past decade, gold nanoparticles have attracted strong interest from the nanobiotechnological community owing to the significant progress made in robust and easy-to-make synthesis technologies, in surface functionalization, and in promising biomedical applications. These include bioimaging, gene diagnostics, analytical sensing, photothermal treatment of tumors, and targeted delivery of various biomolecular and chemical cargos. For the last-named application, gold nanoparticles should be properly fabricated to deliver the cargo into the targeted cells through effective endocytosis. In this review, we discuss recent progress in understanding the selective penetration of gold nanoparticles into immune cells. The interaction of gold nanoparticles with immune cell receptors is discussed. As distinct from other published reviews, we present a summary of the immunological properties of gold nanoparticles. This review also summarizes what is known about the application of gold nanoparticles as an antigen carrier and adjuvant in immunization for the preparation of antibodies in vivo . For each of the above topics, the basic principles, recent advances, and current challenges are discussed. Thus, this review presents a detailed analysis of data on interaction of gold nanoparticles with immune cells. Emphasis is placed on the systematization of data over production of antibodies by using gold nanoparticles and adjuvant properties of gold nanoparticles. Specifically, we start our discussion with current data on interaction of various gold nanoparticles with immune cells. The next section describes existing technologies to improve production of antibodies in vivo by using gold nanoparticles conjugated with specific ligands. Finally, we describe what is known about adjuvant properties of bare gold or functionalized nanoparticles. In the Conclusion section, we present a short summary of reported data and some challenges and perspectives.

  15. The extractive metallurgy of gold

    Energy Technology Data Exchange (ETDEWEB)

    Kongolo, K.; Mwema, M.D. [University of Lubumbashi, Zaire, Gecamines Metallurgical Research Centre, Likasi, Zaire, c/o Gecamines Brussels (Belgium)

    1998-12-15

    Moessbauer spectroscopy has been successfully used in investigation of the gold compounds present in ores and the gold species which occur during the process metallurgy of this metal. This paper is a survey of the basic recovery methods and techniques used in extractive metallurgy of gold. Process fundamentals on mineral processing, ore leaching, zinc dust cementation, adsorption on activated carbon, electrowinning and refining are examined. The recovery of gold as a by-product of the copper industry is also described. Alternative processing methods are indicated in order to shed light on new interesting research topics where Moessbauer spectroscopy could be applied.

  16. The extractive metallurgy of gold

    Science.gov (United States)

    Kongolo, K.; Mwema, M. D.

    1998-12-01

    Mössbauer spectroscopy has been successfully used in investigation of the gold compounds present in ores and the gold species which occur during the process metallurgy of this metal. This paper is a survey of the basic recovery methods and techniques used in extractive metallurgy of gold. Process fundamentals on mineral processing, ore leaching, zinc dust cementation, adsorption on activated carbon, electrowinning and refining are examined. The recovery of gold as a by-product of the copper industry is also described. Alternative processing methods are indicated in order to shed light on new interesting research topics where Mössbauer spectroscopy could be applied.

  17. The extractive metallurgy of gold

    International Nuclear Information System (INIS)

    Kongolo, K.; Mwema, M.D.

    1998-01-01

    Moessbauer spectroscopy has been successfully used in investigation of the gold compounds present in ores and the gold species which occur during the process metallurgy of this metal. This paper is a survey of the basic recovery methods and techniques used in extractive metallurgy of gold. Process fundamentals on mineral processing, ore leaching, zinc dust cementation, adsorption on activated carbon, electrowinning and refining are examined. The recovery of gold as a by-product of the copper industry is also described. Alternative processing methods are indicated in order to shed light on new interesting research topics where Moessbauer spectroscopy could be applied

  18. Surface-stabilized gold nanocatalysts

    Science.gov (United States)

    Dai, Sheng [Knoxville, TN; Yan, Wenfu [Oak Ridge, TN

    2009-12-08

    A surface-stabilized gold nanocatalyst includes a solid support having stabilizing surfaces for supporting gold nanoparticles, and a plurality of gold nanoparticles having an average particle size of less than 8 nm disposed on the stabilizing surfaces. The surface-stabilized gold nanocatalyst provides enhanced stability, such as at high temperature under oxygen containing environments. In one embodiment, the solid support is a multi-layer support comprising at least a first layer having a second layer providing the stabilizing surfaces disposed thereon, the first and second layer being chemically distinct.

  19. Accelerators for forming cationic technetium complexes useful as radiodiagnostic images

    International Nuclear Information System (INIS)

    Tweedle, M.F.

    1985-01-01

    This invention relates to compositions for making cationic radiodiagnostic agents and, in particular, to accelerator compounds for labelling such cationic radiodiagnostic agents, kits for preparing such 99m Tc-labelled cationic radiodiagnostic agents with technetium, and methods for labelling such cationic radiodiagnostic agents with technetium

  20. 31 CFR 100.4 - Gold coin and gold certificates in general.

    Science.gov (United States)

    2010-07-01

    ... 31 Money and Finance: Treasury 1 2010-07-01 2010-07-01 false Gold coin and gold certificates in... EXCHANGE OF PAPER CURRENCY AND COIN In General § 100.4 Gold coin and gold certificates in general. Gold coins, and gold certificates of the type issued before January 30, 1934, are exchangeable, as provided...

  1. Intrinsic multistate switching of gold clusters through electrochemical gating

    DEFF Research Database (Denmark)

    Albrecht, Tim; Mertens, S.F.L.; Ulstrup, Jens

    2007-01-01

    The electrochemical behavior of small metal nanoparticles is governed by Coulomb-like charging and equally spaced charge-transfer transitions. Using electrochemical gating at constant bias voltage, we show, for the first time, that individual nanoparticles can be operated as multistate switches i...

  2. Determining gold content

    International Nuclear Information System (INIS)

    Clayton, C.G.; Wormald, M.R.

    1981-01-01

    A method for determining the gold content of a material, comprises irradiating a body of the material with neutrons and determining the intensity of γ-rays having an energy of 279 keV arising from the reaction 179 Au(nn') 179 Au → 279 keV. The apparatus has means for conveying the materials past an assembly, which has a neutron source, which does not produce neutrons having sufficient energy to excite fast neutron reactions in non-auriferous constituents. (author)

  3. Turning lead into gold

    DEFF Research Database (Denmark)

    Jensen, Steffen Moltrup Ernø

    For years the field of entrepreneurship has been blinded by the alchemical promise of turning lead into gold, of finding the ones most likely to become the next Branson, Zuckerberg or Gates. The promise has been created in the midst of political and scientific agendas where certain individuals...... is not to accumulate state or market wealth, but for entrepreneurial skills to become tools towards the liberation of the individual from oppressive systems of control – essentially to add public value rather than economic value. In this presentation I will sketch an anarchist perspective on entrepreneurship, looking...

  4. Determination of Gold from Gold Matrix of North Western Nigeria ...

    African Journals Online (AJOL)

    The research paper presents analytical results of Au, Mn and V concentrations of some Nigerian gold ores using two techniques: epithermal neutron activation analysis (ENAA) and proton induced X-ray emission (PIXE). Fourteen samples were collected from gold fields of North Western Nigeria, prepared separately to a ...

  5. Phosphate-mediated electrochemical adsorption of cisplatin on gold electrodes

    International Nuclear Information System (INIS)

    Kolodziej, Adam; Figueiredo, Marta C.; Koper, Marc T.M.; Fernandez-Trillo, Francisco; Rodriguez, Paramaconi

    2017-01-01

    Highlights: •The potential-dependent adsorption and deposition of cisplatin on polycrystalline gold electrode is mediated by the adsorption of phosphate anions on gold electrode. •Quantitative analysis suggests that the stoichiometry of the phosphate species and the cisplatin adsorbed was 1:1. •Upon reduction of the phosphate-mediated cisplatin adsorption, the platinum deposits are formed by 3D nanoclusters -- Abstract: This manuscript reports the potential-dependent adsorption and deposition of cisplatin on polycrystalline gold electrode. It was found that this process is mediated by the adsorption of phosphate anions on the gold electrode and that the maximum coverage of Pt adsorbed is given by the maximum coverage of phosphate adsorbed at a given potential. The interaction of cisplatin with the phosphate groups was confirmed by in situ FTIR spectroscopy under external reflexion configuration. Quantitative analysis suggests that the stoichiometry of the phosphate species and the cisplatin adsorbed was 1:1. Moreover, the relationship between the charge of the Pt deposited and the charge of the electrochemical surface area of the Pt deposited on the gold electrodes indicates that 3D nanoclusters of a few atoms of Pt were formed over the gold electrode upon the electrochemical reduction of the adsorbed cisplatin. The Pt nanoclusters formed under these conditions were later evaluated for the oxidation of a monolayer of carbon monoxide. The Pt nanoclusters showed a high overpotential for the oxidation of the carbon monoxide monolayer and the high oxidation overpotential was attributed to the absence of adsorption sites for OH species on the Pt clusters: only at potentials where the OH species are adsorbed at the edge between the Pt nanocluster and the gold support, the oxidation of the carbon monoxide on the Pt nanoparticles takes place.

  6. Optical trapping of metal-dielectric nanoparticle clusters near photonic crystal microcavities.

    Science.gov (United States)

    Mejia, Camilo A; Huang, Ningfeng; Povinelli, Michelle L

    2012-09-01

    We predict the formation of optically trapped, metal-dielectric nanoparticle clusters above photonic crystal microcavities. We determine the conditions on particle size and position for a gold particle to be trapped above the microcavity. We then show that strong field redistribution and enhancement near the trapped gold nanoparticle results in secondary trapping sites for a pair of dielectric nanoparticles.

  7. Effect of the physical properties of activated carbon in the gold adsorption from cyanide media

    International Nuclear Information System (INIS)

    Navarro, P.; Vargas, C.

    2010-01-01

    The effect of the physical properties of an activated carbon such as pore size distribution, specific surface, pore average diameter, in the gold adsorption from cyanide solution with the gold to the Au (CN) - 2 form, was studied. To meet the proposed objectives two carbons were studied: carbon A with specific surface of 985 m 2 / g, 57 % of micropores and 1.85 nm as average diameter of pores and carbon B with specific surface of 786 m 2 / g, 27 % and pores of 2.35 nm as average diameter of pores; both granular carbons made from coconut shell. Batch adsorption tests were performed in a reactor of 500 ml of capacity with mechanical stirring at constant temperature. The effect of cations present in the aqueous solutions such as Ca 2 +, Na+, K+ and Li+, the effect of pore size distribution, the effect of average pore diameter and surface area were evaluated in function of the rate and amount of gold adsorbed on the activated carbons denominated as A and B. The results to indicate that the physical properties of an activated carbon are an important factor in the gold adsorption process in terms of rate and amount of adsorbed gold. The carbon B with 786 m 2 / g of specific surface area reached a higher load per unit area (0.02 mg Au/m 2 ) in relation to the carbon B of 985 m 2 / g which had a load of 0.01 mg Au / m 2 , after 6 h of contact carbon-solution. The rate adsorption of gold in both carbons is controlled by mass transfer in the liquid film surrounding the carbon particles to short times or small loads of gold in the particles, far from equilibrium. Applying a first order kinetic model, it was obtained that the ratio of the kinetic constants for carbons A and B, ie (kB / kA), fluctuates in a value of 3 for the different cations in study. In general it is possible to say that the rate adsorption and the amount of adsorbed gold increased with the increase in macropores and with the increasing pore average diameter. The presence of cations favors the gold

  8. Clustering Dycom

    KAUST Repository

    Minku, Leandro L.; Hou, Siqing

    2017-01-01

    baseline WC model is also included in the analysis. Results: Clustering Dycom with K-Means can potentially help to split the CC projects, managing to achieve similar or better predictive performance than Dycom. However, K-Means still requires the number

  9. Transformation of thiolated chitosan-templated gold nanoparticles to huge microcubes

    International Nuclear Information System (INIS)

    Sun, Yudie; Liu, Honglin; Yang, Liangbao; Sun, Bai; Liu, Jinhuai

    2014-01-01

    Graphical abstract: - Highlights: • Mercapto groups were grafted to chitosan molecule by a reactive amine reduction. • Functional polymer with well-defined monomer units controls AuNPs assembly. • Assembled morphologies depend on the ratio of AuNPs to thiolate groups. • Microcubes with side length of ∼20 μm was synthesized through a dialysis step. • A edge-to-middle growth mechanism of gold microcubes was observed. - Abstract: The L-cysteine molecules were successfully grafted to the 2-amino group of chitosan by a reactive amine reduction, and the as-synthesized thiolated chitosan (TC) molecules were used as the templates to direct the self-assembly of gold nanoparticles and induce the transformation of these assemblies to gold microcubes through a deep-going dialysis. We found that the ratio of gold nanoparticles to TC molecules could greatly affect the shape of the assembled clusters. Different stages of these clusters and microstructures during the dialysis process were characterized by scanning electron microscope (SEM), and the microcubes with average side length of about 20 μm were successfully synthesized. According to the morphology evolution of the assembly, it could be concluded that the microcubes were formed from external to internal. The SERS area mapping images of microcubes and some clusters were also collected to study the formation mechanism of gold microcubes. Our work demonstrates a simple and highly effective way to assemble gold nanoparticles into microcubes with unique properties

  10. Transformation of thiolated chitosan-templated gold nanoparticles to huge microcubes

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Yudie [School of Chemistry and Materials Science, University of Science and Technology of China, Hefei 230026 (China); Institute of Intelligent Machines, Chinese Academy of Sciences, Hefei 230031 (China); Liu, Honglin, E-mail: hlliu@iim.ac.cn [Institute of Intelligent Machines, Chinese Academy of Sciences, Hefei 230031 (China); Yang, Liangbao, E-mail: lbyang@iim.ac.cn [Institute of Intelligent Machines, Chinese Academy of Sciences, Hefei 230031 (China); Sun, Bai; Liu, Jinhuai [Institute of Intelligent Machines, Chinese Academy of Sciences, Hefei 230031 (China)

    2014-05-01

    Graphical abstract: - Highlights: • Mercapto groups were grafted to chitosan molecule by a reactive amine reduction. • Functional polymer with well-defined monomer units controls AuNPs assembly. • Assembled morphologies depend on the ratio of AuNPs to thiolate groups. • Microcubes with side length of ∼20 μm was synthesized through a dialysis step. • A edge-to-middle growth mechanism of gold microcubes was observed. - Abstract: The L-cysteine molecules were successfully grafted to the 2-amino group of chitosan by a reactive amine reduction, and the as-synthesized thiolated chitosan (TC) molecules were used as the templates to direct the self-assembly of gold nanoparticles and induce the transformation of these assemblies to gold microcubes through a deep-going dialysis. We found that the ratio of gold nanoparticles to TC molecules could greatly affect the shape of the assembled clusters. Different stages of these clusters and microstructures during the dialysis process were characterized by scanning electron microscope (SEM), and the microcubes with average side length of about 20 μm were successfully synthesized. According to the morphology evolution of the assembly, it could be concluded that the microcubes were formed from external to internal. The SERS area mapping images of microcubes and some clusters were also collected to study the formation mechanism of gold microcubes. Our work demonstrates a simple and highly effective way to assemble gold nanoparticles into microcubes with unique properties.

  11. Melting of gold microclusters

    International Nuclear Information System (INIS)

    Garzon, I.L.; Jellinek, J.

    1991-01-01

    The transition from solid-like to liquid-like behavior in Au n , n=6, 7, 13, clusters is studied using molecular dynamics simulations. A Gupta-type potential with all-neighbour interactions is employed to incorporate n-body effects. The melting-like transition is described in terms of short-time averages of the kinetic energy per particle, root-mean-square bond length fluctuations and mean square displacements. A comparison between melting temperatures of Au n and Ni n clusters is presented. (orig.)

  12. Gas phase chemistry of N-benzylbenzamides with silver(I) cations: characterization of benzylsilver cation.

    Science.gov (United States)

    Sun, Hezhi; Jin, Zhe; Quan, Hong; Sun, Cuirong; Pan, Yuanjiang

    2015-03-07

    The benzylsilver cation which emerges from the collisional dissociation of silver(I)-N-benzylbenzamide complexes was characterized by deuterium-labeling experiments, theoretical calculations, breakdown curves and substituent effects. The nucleophilic attack of the carbonyl oxygen on an α-hydrogen results in the generation of the benzylsilver cation, which is competitive to the AgH loss with the α-hydrogen.

  13. A combined mechanistic and computational study of the gold(I)-catalyzed formation of substituted indenes.

    Science.gov (United States)

    Nun, Pierrick; Gaillard, Sylvain; Poater, Albert; Cavallo, Luigi; Nolan, Steven P

    2011-01-07

    Substituted indenes can be prepared after a sequence [1,3] O-acyl shift-hydroarylation-[1,3] O-acyl shift. Each step is catalyzed by a cationic NHC-Gold(I) species generated in situ after reaction between [(IPr)AuOH] and HBF(4)·OEt(2). This interesting silver-free way is fully supported by a computational study justifying the formation of each intermediate.

  14. Post-Ugi gold-catalyzed diastereoselective domino cyclization for the synthesis of diversely substituted spiroindolines

    Directory of Open Access Journals (Sweden)

    Amit Kumar

    2013-10-01

    Full Text Available An Ugi four-component reaction of propargylamine with 3-formylindole and various acids and isonitriles produces adducts which are subjected to a cationic gold-catalyzed diastereoselective domino cyclization to furnish diversely substituted spiroindolines. All the reactions run via an exo-dig attack in the hydroarylation step followed by an intramolecular diastereoselective trapping of the imminium ion. The whole sequence is atom economic and the application of a multicomponent reaction assures diversity.

  15. Reactivity of niobium cluster anions with nitrogen and carbon monoxide

    Science.gov (United States)

    Mwakapumba, Joseph; Ervin, Kent M.

    1997-02-01

    Reactions of small niobium cluster anions, Nbn-(n = 2-7), with CO and N2 are investigated using a flow tube reactor (flowing afterglow) apparatus. Carbon monoxide chemisorption on niobium cluster anions occurs with faster reaction rates than nitrogen chemisorption on corresponding cluster sizes. N2 addition to niobium cluster anions is much more size-selective than is CO addition. These general trends follow those reported in the literature for reactions of neutral and cationic niobium clusters with CO and N2. Extensive fragmentation of the clusters is observed upon chemisorption. A small fraction of the larger clusters survive and sequentially add multiple CO or N2 units without fragmentation. However, chemisorption saturation is not reached at the experimentally accessible pressure and reagent concentration ranges. The thermochemistry of the adsorption processes and the nature of the adsorbed species, molecular or dissociated, are discussed.

  16. Interfacial Structures of Trihexyltetradecylphosphonium-bis(mandelato)borate Ionic Liquid Confined between Gold Electrodes.

    Science.gov (United States)

    Wang, Yong-Lei; Golets, Mikhail; Li, Bin; Sarman, Sten; Laaksonen, Aatto

    2017-02-08

    Atomistic molecular dynamics simulations have been performed to study microscopic the interfacial ionic structures, molecular arrangements, and orientational preferences of trihexyltetradecylphosphonium-bis(mandelato)borate ([P 6,6,6,14 ][BMB]) ionic liquid confined between neutral and charged gold electrodes. It was found that both [P 6,6,6,14 ] cations and [BMB] anions are coabsorbed onto neutral electrodes at different temperatures. The hexyl and tetradecyl chains in [P 6,6,6,14 ] cations lie preferentially flat on neutral electrodes. The oxalato and phenyl rings in [BMB] anions are characterized by alternative parallel-perpendicular orientations in the mixed innermost ionic layer adjacent to neutral electrodes. An increase in temperature has a marginal effect on the interfacial ionic structures and molecular orientations of [P 6,6,6,14 ][BMB] ionic species in a confined environment. Electrifying gold electrodes leads to peculiar changes in the interfacial ionic structures and molecular orientational arrangements of [P 6,6,6,14 ] cations and [BMB] anions in negatively and positively charged gold electrodes, respectively. As surface charge density increases (but lower than 20 μC/cm 2 ), the layer thickness of the mixed innermost interfacial layer gradually increases due to a consecutive accumulation of [P 6,6,6,14 ] cations and [BMB] anions at negatively and positively charged electrodes, respectively, before the formation of distinct cationic and anionic innermost layers. Meanwhile, the molecular orientations of two oxalato rings in the same [BMB] anions change gradually from a parallel-perpendicular feature to being partially characterized by a tilted arrangement at an angle of 45° from the electrodes and finally to a dominant parallel coordination pattern along positively charged electrodes. Distinctive interfacial distribution patterns are also observed accordingly for phenyl rings that are directly connected to neighboring oxalato rings in [BMB] anions.

  17. Effect of Divalent Cations on RED Performance and Cation Exchange Membrane Selection to Enhance Power Densities.

    Science.gov (United States)

    Rijnaarts, Timon; Huerta, Elisa; van Baak, Willem; Nijmeijer, Kitty

    2017-11-07

    Reverse electrodialysis (RED) is a membrane-based renewable energy technology that can harvest energy from salinity gradients. The anticipated feed streams are natural river and seawater, both of which contain not only monovalent ions but also divalent ions. However, RED using feed streams containing divalent ions experiences lower power densities because of both uphill transport and increased membrane resistance. In this study, we investigate the effects of divalent cations (Mg 2+ and Ca 2+ ) on RED and demonstrate the mitigation of those effects using both novel and existing commercial cation exchange membranes (CEMs). Monovalent-selective Neosepta CMS is known to block divalent cations transport and can therefore mitigate reductions in stack voltage. The new multivalent-permeable Fuji T1 is able to transport divalent cations without a major increase in resistance. Both strategies significantly improve power densities compared to standard-grade CEMs when performing RED using streams containing divalent cations.

  18. Cation Movements during Dehydration and NO2 Desorption in a Ba-Y,FAU zeolite: an in situ Time-resolved X-ray Diffraction Study

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xianqin; Hanson, Jonathan C.; Kwak, Ja Hun; Szanyi, Janos; Peden, Charles HF

    2013-02-28

    Synchrotron-based in situ time-resolved X-ray diffraction and Rietveld analysis were used to probe the interactions between BaY, FAU zeolite frameworks and H2O or NO2 molecules. These results provided information about the migration of the Ba2+ cations in the zeolite framework during dehydration and during NO2 adsorption/desorption processes in a water free zeolite. In the hydrated structure water molecules form four double rings of hexagonal ice-like clusters [(H2O)6] in the 12-ring openings of the super-cage. These water rings interacted with the cations and the zeolite framework through four cation/water clusters centered over the four 6-membered rings of the super-cage (site II). Interpenetrating tetrahedral water clusters [(H2O)4] and tetrahedral Ba+2 cation clusters were observed in the sodalite cage. Consistent with the reported FT-IR results, three different ionic NOx species (NO+, NO+-NO2, and NO3-) were observed following NO2 adsorption by the dehydrated Ba-Y,FAU zeolite. The structure of the water and the NOx species were correlated with the interactions between the adsorbates, the cations, and the framework. The population of Ba2+ ions at different cationic positions strongly depended on the amount of bound water or NOx species. Both dehydration and NO2 adsorption/desorption resulted in facile migration of Ba2+ ions among the different cationic positions. Data obtained in this work have provided direct evidence for the Ba2+ cation migration to accommodate the binding of gas molecules. This important feature may play a pivotal role in the strong binding of NO2 to Ba-Y,FAU zeolite, a prerequisite for high catalytic activity in lean NOx reduction catalysis.

  19. Activation analysis in gold industry

    International Nuclear Information System (INIS)

    Kist, A. A.

    2003-01-01

    Nuclear techniques and methods were, are, and will be very important for many fields of science, agriculture, industry, etc. Among other examples one can remember role of the nuclear medicine (radiotherapy and radiodiagnostic methods) or semiconductors (communication, computing, information, etc.) which industrial production has been on initial stage based on activation analysis. One of very illustrative examples is application of nuclear methods in gold industry. This is given by favorable nuclear properties of gold. Uzbekistan is one of the main producers of gold. Open-cast mining and hydro metallurgic extraction (using leaching by cyanide and sorption by ion-exchange resin) is the mostly used technology. The typical gold ores are sulfide and contain elevated concentration of As and Sb. That needs special technology of gold extraction. Importance of gold for Uzbekistan economy is a reason why for many years there are carried out studies concerning to gold production. These studies include also nuclear methods and their results are successfully used in gold industry. The present paper gives a brief overview for period of 25 years. For many reasons most of these studies were not published before completely. Despite some results are obtained decades ago we decided to present the overview as an example how nuclear methods can cover requirements of the whole process. We are trying to sort these studies according to methods and applications

  20. Forging Colloidal Nanostructures via Cation Exchange Reactions.

    Science.gov (United States)

    De Trizio, Luca; Manna, Liberato

    2016-09-28

    Among the various postsynthesis treatments of colloidal nanocrystals that have been developed to date, transformations by cation exchange have recently emerged as an extremely versatile tool that has given access to a wide variety of materials and nanostructures. One notable example in this direction is represented by partial cation exchange, by which preformed nanocrystals can be either transformed to alloy nanocrystals or to various types of nanoheterostructures possessing core/shell, segmented, or striped architectures. In this review, we provide an up to date overview of the complex colloidal nanostructures that could be prepared so far by cation exchange. At the same time, the review gives an account of the fundamental thermodynamic and kinetic parameters governing these types of reactions, as they are currently understood, and outlines the main open issues and possible future developments in the field.

  1. Forging Colloidal Nanostructures via Cation Exchange Reactions

    Science.gov (United States)

    2016-01-01

    Among the various postsynthesis treatments of colloidal nanocrystals that have been developed to date, transformations by cation exchange have recently emerged as an extremely versatile tool that has given access to a wide variety of materials and nanostructures. One notable example in this direction is represented by partial cation exchange, by which preformed nanocrystals can be either transformed to alloy nanocrystals or to various types of nanoheterostructures possessing core/shell, segmented, or striped architectures. In this review, we provide an up to date overview of the complex colloidal nanostructures that could be prepared so far by cation exchange. At the same time, the review gives an account of the fundamental thermodynamic and kinetic parameters governing these types of reactions, as they are currently understood, and outlines the main open issues and possible future developments in the field. PMID:26891471

  2. Cluster forcing

    DEFF Research Database (Denmark)

    Christensen, Thomas Budde

    The cluster theory attributed to Michael Porter has significantly influenced industrial policies in countries across Europe and North America since the beginning of the 1990s. Institutions such as the EU, OECD and the World Bank and governments in countries such as the UK, France, The Netherlands...... or management. Both the Accelerate Wales and the Accelerate Cluster programmes target this issue by trying to establish networks between companies that can be used to supply knowledge from research institutions to manufacturing companies. The paper concludes that public sector interventions can make...... businesses. The universities were not considered by the participating companies to be important parts of the local business environment and inputs from universities did not appear to be an important source to access knowledge about new product development or new techniques in production, distribution...

  3. Regional Innovation Clusters

    Data.gov (United States)

    Small Business Administration — The Regional Innovation Clusters serve a diverse group of sectors and geographies. Three of the initial pilot clusters, termed Advanced Defense Technology clusters,...

  4. Colorimetric gold nanoparticles-based aptasensors

    Directory of Open Access Journals (Sweden)

    Rezavn Yazdian-Robati

    2018-01-01

    Full Text Available Recognition of different agents including chemical and biological plays important role in forensic, biomedical and environmentalfield.In recent decades, nanotechnology and nano materials had a high impact on development of sensors. Using  nanomaterials in construction of biosensors can effectively improve the Sensitivity and other features of biosensors. Different type of nanostructures including nanotubes, nanodiamonds, thin films ,nanorods, nanoparticles(NP, nanofibers andvarious clusters have been explored and applied in construction of biosensors. Among nanomaterials mentioned above, gold nanoparticle (GNPas a new class of unique fluorescence quenchers, is receiving significant attention in developing of optical biosensors because of their unique physical, chemical and biological properties. In this mini review, we discussed the use of GNPs in construction of colorimetric aptasensorsas a class of optical sensors for detection of antibiotics, toxins and infection diseases.

  5. Cluster analysis

    OpenAIRE

    Mucha, Hans-Joachim; Sofyan, Hizir

    2000-01-01

    As an explorative technique, duster analysis provides a description or a reduction in the dimension of the data. It classifies a set of observations into two or more mutually exclusive unknown groups based on combinations of many variables. Its aim is to construct groups in such a way that the profiles of objects in the same groups are relatively homogenous whereas the profiles of objects in different groups are relatively heterogeneous. Clustering is distinct from classification techniques, ...

  6. Determination of phosphorus in gold or silver brazing alloys

    International Nuclear Information System (INIS)

    Antepenko, R.J.

    1976-01-01

    A spectrophotometric method has been devised for measuring microgram levels of phosphorus in brazing alloys of gold or silver alloys is normally measured by solid mass spectrometry, but the high nickel concentration produces a double ionized nickel spectral interference. The described procedures is based upon the formation of molybdovandophosphoric acid when a molybdate solution is added to an acidic solution containing orthophosphate and vanadate ions. The optimum acidity for forming the yellow colored product is 0.5 N hydrochloric acid. The working concentration range is from 0.1 to 1 ppm phosphorus using 100-mm cells and measuring the absorbance at 460 nm. The sample preparation procedure employs aqua regia to dissolve the alloy oxidize the phosphorus to orthophosphate. Cation-exchange chromatography is used to remove nickel ions and anion-exchange and chromatography to remove gold ions as the chloride complex. Excellent recoveries are obtained for standard phosphorus solutions run through the sample procedure. The procedure is applicable to a variety of gold or silver braze alloys requiring phosphorus analysis

  7. Cationic Au Nanoparticle Binding with Plasma Membrane-like Lipid Bilayers: Potential Mechanism for Spontaneous Permeation to Cells Revealed by Atomistic Simulations

    DEFF Research Database (Denmark)

    Heikkila, E.; Martinez-Seara, H.; Gurtovenko, A. A.

    2014-01-01

    Despite being chemically inert as a bulk material, nanoscale gold can pose harmful side effects to living organisms. In particular, cationic Au nanoparticles (AuNP+) of 2 nm diameter or less permeate readily through plasma membranes and induce cell death. We report atomistic simulations of cationic...... to be governed by cooperative effects where AuNP+, counterions, water, and the two membrane leaflets all contribute. On the extracellular side, we find that the nanoparticle has to cross a free energy barrier of about 5 k(B)T prior forming a stable contact with the membrane. This results in a rearrangement...

  8. Local structures of ionic liquids in the presence of gold under high pressures

    Directory of Open Access Journals (Sweden)

    Hai-Chou Chang

    2013-03-01

    Full Text Available The interactions between ionic liquid ([EMI][TFS] and gold surfaces have been investigated via the application of pressures up to ca. 2 GPa. Comparing the spectral features of [EMI][TFS]/gold with those of pure [EMI][TFS], no appreciable changes of C-H bands in the presence of gold powders were observed under ambient pressure. Nevertheless, the imidazolium C-H bands display red shifts in frequency as the [EMI][TFS] / Au mixture was compressed to the pressure above 1.4 GPa and a new alkyl C-H band at ca. 3016 cm−1 was also revealed. These spectral changes, being related to the addition of gold powders and pressure elevation, should be attributed to the local structural changes of C-H groups caused by pressure-enhanced interfacial interactions between [EMI][TFS] and Au. Gold powders tend to induce the changes in hydrogen bonding structures of imidazolium C2-H group under high pressures. The pressure-dependent spectral features in the asymmetric SO3 stretching region display band-narrowing and minor local structural changes induced by the presence of gold particles under high pressures. These observations suggest that Au powders perturb structural equilibrium of C-H groups of cations under high pressures.

  9. Effect of gold nanoparticle on stability of the DNA molecule: A study of molecular dynamics simulation.

    Science.gov (United States)

    Izanloo, Cobra

    2017-09-02

    An understanding of the mechanism of DNA interactions with gold nanoparticles is useful in today medicine applications. We have performed a molecular dynamics simulation on a B-DNA duplex (CCTCAGGCCTCC) in the vicinity of a gold nanoparticle with a truncated octahedron structure composed of 201 gold atoms (diameter ∼1.8 nm) to investigate gold nanoparticle (GNP) effects on the stability of DNA. During simulation, the nanoparticle is closed to DNA and phosphate groups direct the particles into the major grooves of the DNA molecule. Because of peeling and untwisting states that are occur at end of DNA, the nucleotide base lies flat on the surface of GNP. The configuration entropy is estimated using the covariance matrix of atom-positional fluctuations for different bases. The results show that when a gold nanoparticle has interaction with DNA, entropy increases. The results of conformational energy and the hydrogen bond numbers for DNA indicated that DNA becomes unstable in the vicinity of a gold nanoparticle. The radial distribution function was calculated for water hydrogen-phosphate oxygen pairs. Almost for all nucleotide, the presence of a nanoparticle around DNA caused water molecules to be released from the DNA duplex and cations were close to the DNA.

  10. Stealing the Gold

    International Nuclear Information System (INIS)

    Whittington, S G

    2005-01-01

    Stealing the Gold presents a survey of some of the most exciting topics in condensed matter physics today, from the perspective of the pioneering work of Sam Edwards. Original articles from leaders in the field, including several Nobel laureates, highlight the historical development as well as new and emerging areas. This book would be of interest to graduate students and researchers in condensed matter physics, statistical physics and theoretical physics. Over the course of nearly half a century, Sam Edwards has led the field of condensed matter physics in new directions, ranging from the electronic and statistical properties of disordered materials to the mechanical properties of granular materials. Along the way he has provided seminal contributions to fluid mechanics, polymer science, surface science and statistical mechanics. This volume celebrates the immense scope of his influence by presenting a collection of original articles by recognized leaders in theoretical physics, including two Nobel laureates and a Fields medalist, which describe the genesis, evolution and future prospects of the various sub-fields of condensed matter theory, along with reprints of a selection of Edwards' seminal papers that helped give birth to the subject. Stealing the Gold, Edwards' favourite caricature of the relationship between theoretical physicists and nature, will be of singular interest to graduate students looking for an overview of some of the most exciting areas of theoretical physics, as well as to researchers in condensed matter physics looking for a comprehensive, broad and uniquely incisive snapshot of their subject at the dawn of the 21st century. (book review)

  11. A multivariate geostatistical methodology to delineate areas of potential interest for future sedimentary gold exploration.

    Science.gov (United States)

    Goovaerts, P; Albuquerque, Teresa; Antunes, Margarida

    2016-11-01

    This paper describes a multivariate geostatistical methodology to delineate areas of potential interest for future sedimentary gold exploration, with an application to an abandoned sedimentary gold mining region in Portugal. The main challenge was the existence of only a dozen gold measurements confined to the grounds of the old gold mines, which precluded the application of traditional interpolation techniques, such as cokriging. The analysis could, however, capitalize on 376 stream sediment samples that were analyzed for twenty two elements. Gold (Au) was first predicted at all 376 locations using linear regression (R 2 =0.798) and four metals (Fe, As, Sn and W), which are known to be mostly associated with the local gold's paragenesis. One hundred realizations of the spatial distribution of gold content were generated using sequential indicator simulation and a soft indicator coding of regression estimates, to supplement the hard indicator coding of gold measurements. Each simulated map then underwent a local cluster analysis to identify significant aggregates of low or high values. The one hundred classified maps were processed to derive the most likely classification of each simulated node and the associated probability of occurrence. Examining the distribution of the hot-spots and cold-spots reveals a clear enrichment in Au along the Erges River downstream from the old sedimentary mineralization.

  12. Scanning tunneling microscopy studies of glucose oxidase on gold surface

    International Nuclear Information System (INIS)

    Losic, D.; Shapter, J.G.; Gooding, J.J.

    2002-01-01

    Full text: Three immobilization methods have been used for scanning tunneling microscopy (STM) studies of glucose oxidase (GOD) on gold. They are based on a) physical adsorption from solution, b) microcontact printing and c) covalent bonding onto self-assembled monolayers (SAM) of 3-mercaptopropionic acid (MPA). The STM images are used to provide information about the organization of individual GOD molecules and more densely packed monolayers of GOD on electrode surfaces, thus providing information of the role of interfacial structure on biosensor performance. The use of atomically flat gold substrates enables easy distinction of deposited enzyme features from the flat gold substrate. Microcontact printing is found to be a more reliable method than adsorption from solution for preparing individual GOD molecules on the gold surface STM images of printed samples reveal two different shapes of native GOD molecules. One is a butterfly shape with dimensions of 10 ± 1 nm x 6 ± 1 nm, assigned to the lying position of molecule while the second is an approximately spherical shape with dimensions of 6.5 ± 1 nm x 5 ± 1nm assigned to a standing position. Isolated clusters of 5 to 6 GOD molecules are also observed. With monolayer coverage, GOD molecules exhibit a tendency to organize themselves into a two dimensional array with adequate sample stability to obtain high-resolution STM images. Within these two-dimensional arrays are clearly seen repeating clusters of five to six enzyme molecules in a unit STM imaging of GOD monolayers covalently immobilized onto SAM (MPA) are considerably more difficult than when the enzyme is adsorbed directly onto the metal. Cluster structures are observed both high and low coverage despite the fact that native GOD is a negatively charged molecule. Copyright (2002) Australian Society for Electron Microscopy Inc

  13. In Situ Scanning Tunneling Microscopy Topography Changes of Gold (111) in Aqueous Sulfuric Acid Produced by Electrochemical Surface Oxidation and Reduction and Relaxation Phenomena

    Science.gov (United States)

    Pasquale, M. A.; Nieto, F. J. Rodríguez; Arvia, A. J.

    The electrochemical formation and reduction of O-layers on gold (111) films in 1 m sulfuric acid under different potentiodynamic routines are investigated utilizing in situ scanning tunneling microscopy. The surface dynamics is interpreted considering the anodic and cathodic reaction pathways recently proposed complemented with concurrent relaxation phenomena occurring after gold (111) lattice mild disruption (one gold atom deep) and moderate disruption (several atoms deep). The dynamics of both oxidized and reduced gold topographies depends on the potentiodynamic routine utilized to form OH/O surface species. The topography resulting from a mild oxidative disruption is dominated by quasi-2D holes and hillocks of the order of 5 nm, involving about 500-600 gold atoms each, and their coalescence. A cooperative turnover process at the O-layer, in which the anion ad-layer and interfacial water play a key role, determines the oxidized surface topography. The reduction of these O-layers results in gold clusters, their features depending on the applied potential routine. A moderate oxidative disruption produces a surface topography of hillocks and holes several gold atoms high and deep, respectively. The subsequent reduction leads to a spinodal gold pattern. Concurrent coalescence appears to be the result of an Ostwald ripening that involves the surface diffusion of both gold atoms and clusters. These processes produce an increase in surface roughness and an incipient gold faceting. The dynamics of different topographies can be qualitatively explained employing the arguments from colloidal science theory. For 1.1 V ≤ E ≅ Epzc weak electrostatic repulsions favor gold atom/cluster coalescence, whereas for E < Epzc the attenuated electrostatic repulsions among gold surfaces stabilize small clusters over the substrate producing string-like patterns.

  14. Restructuring of a peat in interaction with multivalent cations: effect of cation type and aging time.

    Directory of Open Access Journals (Sweden)

    Yamuna Kunhi Mouvenchery

    Full Text Available It is assumed to be common knowledge that multivalent cations cross-link soil organic matter (SOM molecules via cation bridges (CaB. The concept has not been explicitly demonstrated in solid SOM by targeted experiments, yet. Therefore, the requirements for and characteristics of CaB remain unidentified. In this study, a combined experimental and molecular modeling approach was adopted to investigate the interaction of cations on a peat OM from physicochemical perspective. Before treatment with salt solutions of Al(3+, Ca(2+ or Na(+, respectively, the original exchangeable cations were removed using cation exchange resin. Cation treatment was conducted at two different values of pH prior to adjusting pH to 4.1. Cation sorption is slower (>>2 h than deprotonation of functional groups (<2 h and was described by a Langmuir model. The maximum uptake increased with pH of cation addition and decreased with increasing cation valency. Sorption coefficients were similar for all cations and at both pH. This contradicts the general expectations for electrostatic interactions, suggesting that not only the interaction chemistry but also spatial distribution of functional groups in OM determines binding of cations in this peat. The reaction of contact angle, matrix rigidity due to water molecule bridges (WaMB and molecular mobility of water (NMR analysis suggested that cross-linking via CaB has low relevance in this peat. This unexpected finding is probably due to the low cation exchange capacity, resulting in low abundance of charged functionalities. Molecular modeling demonstrates that large average distances between functionalities (∼3 nm in this peat cannot be bridged by CaB-WaMB associations. However, aging strongly increased matrix rigidity, suggesting successive increase of WaMB size to connect functionalities and thus increasing degree of cross-linking by CaB-WaMB associations. Results thus demonstrated that the physicochemical structure of OM is

  15. Vacancy Clusters on Surfaces of Au Nanoparticles Embedded in MgO

    International Nuclear Information System (INIS)

    Xu, Jun; Mills, A. P. Jr.; Ueda, A.; Henderson, D. O.; Suzuki, R.; Ishibashi, S.

    1999-01-01

    MeV implantation of gold ions into MgO(100) followed by annealing is a method to form gold nanoparticles for obtaining modified optical properties. We show from variable-energy positron spectroscopy that clusters of 2 Mg and 2 O vacancies (v 4 ) are attached to the gold nanoparticle surfaces within the projected range (R p ) . We also find that v 4 vacancy clusters are created at depths less than R p , and extend into the region greater than R p due to damage induced by knock-on collisions. (c) 1999 The American Physical Society

  16. Low-temperature positron lifetime and Doppler-broadening measurements for single-crystal nickel oxide containing cation vacancies

    International Nuclear Information System (INIS)

    Waber, J.T.; Snead, C.L. Jr.; Lynn, K.G.

    1985-01-01

    Lifetime and Doppler-broadening measurements for positron annihilation in substoichiometric nickelous oxide have been made concomitantly from liquid-helium to room temperature. The concentration of cation vacancies is readily controlled by altering the ambient oxygen pressure while annealing the crystals at 1673 0 K. It was found that neither of the three lifetimes observed or their relative intensities varied significantly with the oxygen pressure, and the bulk rate only increased slightly when the specimen was cooled from room to liquid-helium temperatures. These results are interpreted as indicating that some of the positrons are trapped by the existing cation vacancies and a smaller fraction by vacancy clusters

  17. Adsorption of cationic amylopectin on microcrystalline cellulose.

    NARCIS (Netherlands)

    Steeg, van de H.G.M.; Keizer, de A.; Cohen Stuart, M.A.; Bijsterbosch, B.H.

    1993-01-01

    The effects of electrolyte concentration and pH on the adsorption of cationic amylopectin on microcrystalline cellulose were investigated. The adsorbed amount in the pseudo-plateau of the isotherm showed a maximum as a function of the electrolyte concentration. We compared the data with a recent

  18. Alkynylcarbenium ions and related unsaturated cations

    Energy Technology Data Exchange (ETDEWEB)

    Lukyanov, Sergey M; Koblik, Alla V; Muradyan, Lyudmila A [Institute of Physical and Organic Chemistry, Rostov State University, Rostov-on-Don (Russian Federation)

    1998-10-31

    Published data on carbenium ions containing carbon-carbon triple bonds both directly conjugated with the carbenium centre and separated from it are surveyed and described systematically. Ammonium, diazonium, iminium, phosphonium and iodonium cations containing alkynyl groups, which can be regarded as heteroanalogues of alkynylcarbenium ions, are also considered. The bibliography includes 283 references.

  19. Alkynylcarbenium ions and related unsaturated cations

    International Nuclear Information System (INIS)

    Lukyanov, Sergey M; Koblik, Alla V; Muradyan, Lyudmila A

    1998-01-01

    Published data on carbenium ions containing carbon-carbon triple bonds both directly conjugated with the carbenium centre and separated from it are surveyed and described systematically. Ammonium, diazonium, iminium, phosphonium and iodonium cations containing alkynyl groups, which can be regarded as heteroanalogues of alkynylcarbenium ions, are also considered. The bibliography includes 283 references

  20. Effect of cations on the hydrated proton.

    Science.gov (United States)

    Ottosson, Niklas; Hunger, Johannes; Bakker, Huib J

    2014-09-17

    We report on a strong nonadditive effect of protons and other cations on the structural dynamics of liquid water, which is revealed using dielectric relaxation spectroscopy in the frequency range of 1-50 GHz. For pure acid solutions, protons are known to have a strong structuring effect on water, leading to a pronounced decrease of the dielectric response. We observe that this structuring is reduced when protons are cosolvated with salts. This reduction is exclusively observed for combinations of protons with other ions; for all studied solutions of cosolvated salts, the effect on the structural dynamics of water is observed to be purely additive, even up to high concentrations. We derive an empirical model that quantitatively describes the nonadditive effect of cosolvated protons and cations. We argue that the effect can be explained from the special character of the proton in water and that Coulomb fields exerted by other cations, in particular doubly charged cations like Mg(2+)aq and Ca(2+)aq, induce a localization of the H(+)aq hydration structures.

  1. Mixed cation effect in sodium aluminosilicate glasses

    DEFF Research Database (Denmark)

    Kjeldsen, Jonas; Smedskjær, Morten Mattrup; Mauro, John C.

    , network structure, and the resistances associated with the deformation processes in mixed cation glasses by partially substituting magnesium for calcium and calcium for lithium in sodium aluminosilicate glasses. We use Raman and 27Al NMR spectroscopies to obtain insights into the structural...

  2. Cationic flotation of some lithium ores

    International Nuclear Information System (INIS)

    Valadao, G.E.S.; Peres, A.E.C.; Silva, H.C. da

    1984-01-01

    The cationic flotation of some lithium ores (spodumene, amblygonite, petalite, lepidolite) is studied by the measure of zeta potential and micro-flotation tests in Hallimond tube. The effect of some modifier agents (corn starch, meta sodium silicate) on the lithium flotation is studied. (M.A.C.) [pt

  3. Letter: OCCO*+, NNCO*+ and NNNN*+ radical cations.

    Science.gov (United States)

    Flammang, R; Srinivas, R; Nguyen, M T; Gerbaux, P

    2007-01-01

    Chemical ionization of a mixture of nitrogen and carbon monoxide produces three stable isobaric species at m/z 56: OCCO, OCNN and NNNN radical cations. Separated at increased resolution, these ions are readily identified by collisional activation. Neutralization-reionization experiments performed on two different mass spectrometers have not allowed the detection of any recovery signals for the corresponding neutrals.

  4. Al cation induces aggregation of serum proteins.

    Science.gov (United States)

    Chanphai, P; Kreplak, L; Tajmir-Riahi, H A

    2017-07-15

    Al cation is known to induce protein fibrillation and causes several neurodegenerative disorders. We report the spectroscopic, thermodynamic analysis and AFM imaging for the Al cation binding process with human serum albumin (HSA), bovine serum albumin (BSA) and milk beta-lactoglobulin (b-LG) in aqueous solution at physiological pH. Hydrophobicity played a major role in Al-protein interactions with more hydrophobic b-LG forming stronger Al-protein complexes. Thermodynamic parameters ΔS, ΔH and ΔG showed Al-protein bindings occur via hydrophobic and H-bonding contacts for b-LG, while van der Waals and H-bonding interactions prevail in HSA and BSA adducts. AFM clearly indicated that aluminum cations are able to force BSA and b-LG into larger or more robust aggregates than HSA, with HSA 4±0.2 (SE, n=801) proteins per aggregate, for BSA 17±2 (SE, n=148), and for b-LG 12±3 (SE, n=151). Thioflavin T test showed no major protein fibrillation in the presence of Al cation. Al complexation induced major alterations of protein conformations with the order of perturbations b-LG>BSA>HSA. Copyright © 2017 Elsevier B.V. All rights reserved.

  5. Chemical reactivity of cation-exchanged zeolites

    NARCIS (Netherlands)

    Pidko, E.A.

    2008-01-01

    Zeolites modified with metal cations have been extensively studied during the last two decades because of their wide application in different technologically important fields such as catalysis, adsorption and gas separation. Contrary to the well-understood mechanisms of chemical reactions catalyzed

  6. Directed Assembly of Gold Nanoparticles

    DEFF Research Database (Denmark)

    Westerlund, Axel Rune Fredrik; Bjørnholm, Thomas

    2009-01-01

    As a complement to common "top-down" lithography techniques, "bottom-up" assembly techniques are emerging as promising tools to build nanoscale structures in a predictable way. Gold nanoparticles that are stable and relatively easy to synthesize are important building blocks in many such structures...... due to their useful optical and electronic properties. Programmed assembly of gold nanoparticles in one, two, and three dimensions is therefore of large interest. This review focuses on the progress from the last three years in the field of directed gold nanoparticle and nanorod assembly using...

  7. GOLD and the fixed ratio

    Directory of Open Access Journals (Sweden)

    Vestbo J

    2012-09-01

    Full Text Available Jørgen VestboUniversity of Manchester, Manchester, UKI read with interest the paper entitled "Diagnosis of airway obstruction in the elderly: contribution of the SARA study" by Sorino et al in a recent issue of this journal.1 Being involved in the Global Initiative for Obstructive Lung Diseases (GOLD, it is nice to see the interest sparked by the GOLD strategy document. However, in the paper by Sorino et al, there are a few misunderstandings around GOLD and the fixed ratio (forced expiratory volume in 1 second/forced volume vital capacity < 0.70 that need clarification.View original paper by Sorino and colleagues.

  8. Selective crystallization of cations with crown ethers

    International Nuclear Information System (INIS)

    Heffels, Dennis Egidius

    2014-01-01

    The aim of this work was to study the selectivity and preferences of the incorporation of differently sized cations in the cavities of various crown ethers and the characterization of the resulting compounds. The coordination preferences of crown ethers with different cavities have long been known, and the impact of other effects on the structure formation have increasingly become the focus of attention. In this work a comparative overview of the coordination preferences depending on various factors was undertaken. The focus was mainly on the variation of the cavity of the crown ether in the presence of differently sized cations. In addition, the effects of the solvent and differently coordinating anions have been investigated. Within the framework of this work, basic coordination preferences could be detected with rare earth nitrates, which are affected particularly by the choice of the solvent. The formation of different types of structures could be controlled by varying the conditions such that the incorporation of the cation in the cavity of the crown ether was influenced and the formation of a particular type of structure can be influenced partly by the choice of solvent. In this case no direct preferences for the incorporation into the cavity of the crown ether in relation to the cation size were observed for rare earth cations. However, the coordination of the crown ether leads in each case - for lanthanides - to rather high coordination numbers. A total of five new rare earth complexes and two structural variants could be observed with crown ethers. In the study of the selectivity of the incorporation into the cavity, known structures were also reproduced and further structures were characterized but the crystal structures not entirely solved. With the use of monovalent cations such as potassium, lithium or silver a total of nine new compounds could be synthesized, while no clear preferences for the incorporation of certain cations were detected. The

  9. Understanding the catalytic activity of gold nanoparticles through multi-scale simulations

    DEFF Research Database (Denmark)

    Brodersen, Simon Hedegaard; Vej-Hansen, Ulrik Grønbjerg; Larsen, Britt Hvolbæk

    2011-01-01

    We investigate how the chemical reactivity of gold nanoparticles depends on the cluster size and shape using a combination of simulation techniques at different length scales, enabling us to model at the atomic level the shapes of clusters in the size range relevant for catalysis. The detailed......-coordinated active sites is found, and their reactivities are extracted from models based on Density Functional Theory calculations. This enables us to determine the chemical activity of clusters in the same range of particle sizes that is accessible experimentally. The variation of reactivity with particle size...... is in excellent agreement with experiments, and we conclude that the experimentally observed trends are mostly explained by the high reactivity of under-coordinated corner atoms on the gold clusters. Other effects, such as the effect of the substrate, may influence the reactivities significantly, but the presence...

  10. GOLD predictivity mapping in French Guiana using an expert-guided data-driven approach based on a regional-scale GIS

    Science.gov (United States)

    Cassard, Daniel; Billa, Mario; Lambert, Alain; Picot, Jean-Claude; Husson, Yves

    2008-05-01

    The realistic estimation of gold mining in French Guiana requires including the numerous illegal gold washing activities in predictivity mapping. The combination of a classical approach, based on the algebraic method of Knox-Robinson and Groves, with innovative processing grid-type geochemical and radiometric data, as well as cluster analysis technique provides a better understanding of the structure of studied mineralized areas.

  11. Enhancement of gold recovery using bioleaching from gold concentrate

    Science.gov (United States)

    Choi, S. H.; Cho, K. H.; Kim, B. J.; Choi, N. C.; Park, C. Y.

    2012-04-01

    The gold in refractory ores is encapsulated as fine particles (sometimes at a molecular level) in the crystal structure of the sulfide (typically pyrite with or without arsenopyrite) matrix. This makes it impossible to extract a significant amount of refractory gold by cyanidation since the cyanide solution cannot penetrate the pyrite/arsenopyrite crystals and dissolve gold particles, even after fine grinding. To effectively extract gold from these ores, an oxidative pretreatment is necessary to break down the sulfide matrix. The most popular methods of pretreatment include nitric acid oxidation, roasting, pressure oxidation and biological oxidation by microorganisms. This study investigated the bioleaching efficiency of Au concentrate under batch experimental conditions (adaptation cycles and chemical composition adaptation) using the indigenous acidophilic bacteria collected from gold mine leachate in Sunsin gold mine, Korea. We conducted the batch experiments at two different chemical composition (CuSO4 and ZnSO4), two different adaptation cycles 1'st (3 weeks) and 2'nd (6 weeks). The results showed that the pH in the bacteria inoculating sample decreased than initial condition and Eh increased. In the chemical composition adaptation case, the leached accumulation content of Fe and Pb was exhibited in CuSO4 adaptation bacteria sample more than in ZnSO4 adaptation bacteria samples, possibly due to pre-adaptation effect on chalcopyrite (CuFeS2) in gold concentrate. And after 21 days on the CuSO4 adaptation cycles case, content of Fe and Pb was appeared at 1'st adaptation bacteria sample(Fe - 1.82 and Pb - 25.81 times per control sample) lower than at 2'nd adaptation bacteria sample(Fe - 2.87 and Pb - 62.05 times per control sample). This study indicates that adaptation chemical composition and adaptation cycles can play an important role in bioleaching of gold concentrate in eco-/economic metallurgy process.

  12. X-Ray Spectroscopy of Gold Nanoparticles

    Science.gov (United States)

    Nahar, Sultana N.; Montenegro, M.; Pradhan, A. K.; Pitzer, R.

    2009-06-01

    Inner shell transitions, such as 1s-2p, in heavy elements can absorb or produce hard X-rays, and hence are widely used in nanoparticles. Bio-medical research for cancer treatment has been using heavy element nanoparticles, embeded in malignant tumor, for efficient absorption of irradiated X-rays and leading emission of hard X-rays and energetic electrons to kill the surrounding cells. Ejection of a 1s electron during ionization of the element by absorption of a X-ray photon initiates the Auger cascades of emission of photons and electrons. We have investigated gold nanoparticles for the optimal energy range, below the K-edge (1s) ionization threshold, that corresponds to resonant absorption of X-rays with large attenuation coefficients, orders of magnitude higher over the background as well as to that at K-edge threshold. We applied these attenuation coefficients in Monte Carlo simulation to study the intensities of emission of photons and electrons by Auger cascades. The numerical experiments were carried out in a phantom of water cube with a thin layer, 0.1mm/g, of gold nanoparticles 10 cm inside from the surface using the well-known code Geant4. We will present results on photon and electron emission spectra from passing monochromatic X-ray beams at 67 keV, which is the resonant energy for resonant K_{α} lines, at 82 keV, the K-shell ionization threshold, and at 2 MeV where the resonant effect is non-existent. Our findings show a high peak in the gold nanoparticle absorption curve indicating complete absorption of radiation within the gold layer. The photon and electron emission spectra show resonant features. Acknowledgement: Partially supported by a Large Interdisciplinary Grant award of the Ohio State University and NASA APRA program (SNN). The computational work was carried out on the Cray X1 and Itanium 4 cluster at the Ohio Supercomputer Center, Columbus Ohio. "Resonant X-ray Irradiation of High-Z Nanoparticles For Cancer Theranostics" (refereed

  13. [Noncovalent cation-π interactions--their role in nature].

    Science.gov (United States)

    Fink, Krzysztof; Boratyński, Janusz

    2014-11-07

    Non-covalent interactions play an extremely important role in organisms. The main non-covalent interactions in nature are: ion-ion interactions, dipole-dipole interactions, hydrogen bonds, and van der Waals interactions. A new kind of intermolecular interactions--cation-π interactions--is gaining increasing attention. These interactions occur between a cation and a π system. The main contributors to cation-π interactions are electrostatic, polarization and, to a lesser extent, dispersion interactions. At first, cation-π interactions were studied in a gas phase, with metal cation-aromatic system complexes. The characteristics of these complexes are as follows: an increase of cation atomic number leads to a decrease of interaction energy, and an increase of cation charge leads to an increase of interaction energy. Aromatic amino acids bind with metal cations mainly through interactions with their main chain. Nevertheless, cation-π interaction with a hydrophobic side chain significantly enhances binding energy. In water solutions most cations preferentially interact with water molecules rather than aromatic systems. Cation-π interactions occur in environments with lower accessibility to a polar solvent. Cation-π interactions can have a stabilizing role on the secondary, tertiary and quaternary structure of proteins. These interactions play an important role in substrate or ligand binding sites in many proteins, which should be taken into consideration when the screening of effective inhibitors for these proteins is carried out. Cation-π interactions are abundant and play an important role in many biological processes.

  14. Ultrasmooth, Highly Spherical Monocrystalline Gold Particles for Precision Plasmonics

    KAUST Repository

    Lee, You-Jin

    2013-12-23

    Ultrasmooth, highly spherical monocrystalline gold particles were prepared by a cyclic process of slow growth followed by slow chemical etching, which selectively removes edges and vertices. The etching process effectively makes the surface tension isotropic, so that spheres are favored under quasi-static conditions. It is scalable up to particle sizes of 200 nm or more. The resulting spherical crystals display uniform scattering spectra and consistent optical coupling at small separations, even showing Fano-like resonances in small clusters. The high monodispersity of the particles we demonstrate should facilitate the self-assembly of nanoparticle clusters with uniform optical resonances, which could in turn be used to fabricate optical metafluids. Narrow size distributions are required to control not only the spectral features but also the morphology and yield of clusters in certain assembly schemes. © 2013 American Chemical Society.

  15. In harmony with gold and uranium

    International Nuclear Information System (INIS)

    Anon.

    1983-01-01

    A profile is given on Mr Clive Knobbs as managing director of Harmony gold mine. From March 1 1983 he succeeded as deputy chairman of the group's gold and uranium division, and became the Rand Mines representative on the Gold Producers Committee and the Executive Committee of the Chamber of Mines. The article also takes a look at gold and uranium mining in general

  16. 41 CFR 101-45.002 - Gold.

    Science.gov (United States)

    2010-07-01

    ... 41 Public Contracts and Property Management 2 2010-07-01 2010-07-01 true Gold. 101-45.002 Section... PERSONAL PROPERTY § 101-45.002 Gold. (a) Gold will be sold in accordance with this section and part 102-38 of the Federal Management Regulation. (b) Sales of gold shall be processed to— (1) Use the sealed bid...

  17. A cationic Ag-I(PNPtBu) species acting as PNP transfer agent: Facile synthesis of Pd(PNPtBu)(alkyl) complexes and their reactivity compared to PCPtBu analogues

    NARCIS (Netherlands)

    van der Vlugt, J.I.; Siegler, M.A.; Janssen, M.; Vogt, D.; Spek, A.L.

    2009-01-01

    The straightforward Synthesis of cationic complex 1, [Ag(PNtBu)]BF4 (PNPtBu = 1,2-bis[(di-tert-butylphosphino)methyl]pyridine), and its facile transmetalating properties toward gold and palladium are described. The corresponding Au complex [Au(PNPtBu)](2)(BF4)(2) (2) exists its a dimer in the solid

  18. A cationic Agi( PNPtBu) species acting as PNP transfer agent: facile synthesis of Pd(PNPtBu)(alkyl) complexes and their reactivity compared to PCPtBu analogues

    NARCIS (Netherlands)

    Vlugt, van der J.I.; Siegler, M.A.; Janssen, M.C.C.; Vogt, D.; Spek, A.L.

    2009-01-01

    The straightforward synthesis of cationic complex 1, [Ag(PNPtBu)]BF4 (PNPtBu = 1,2-bis[(di-tert-butylphosphino)methyl]pyridine), and its facile transmetalating properties toward gold and palladium are described. The corresponding Au complex [Au(PNPtBu)]2(BF4)2 (2) exists as a dimer in the solid

  19. Size fraction assaying of gold bearing rocks (for gold extraction) by ...

    African Journals Online (AJOL)

    A novel method has been developed for processing and extraction of gold from gold bearing rocks for use by small-scale gold miners in Ghana. The methodology involved crushing of gold bearing hard rocks to fine particles to form a composite sample and screening at a range of sizes. Gold distribution in the composite ...

  20. Gold--a controversial sensitizer

    DEFF Research Database (Denmark)

    Bruze, M; Andersen, Klaus Ejner

    1999-01-01

    allergy to gold sodium thiosulfate were published at the beginning of the 1990s, the allergic nature of the reported positive patch test reactions to gold was questioned. The major argument for such questioning was the lack of demonstrable clinical relevance in most positive reactors. A major reason......Until recently, gold allergy was considered to be extremely rare. Gold has been used and worshipped for thousands of years without any obvious complaints of skin problems, either in those participating in mining and other ways of prospecting, or in those wearing jewellery. When studies on contact...... for the questioning may have been confusion in differentiating between contact allergy and allergic contact dermatitis. To arrive at a diagnosis of allergic contact dermatitis, 3 steps have, in principle, to be fulfilled: (i) establishment of contact allergy; (ii) demonstration of present exposure; (iii) assessment...

  1. Gold, currencies and market efficiency

    Science.gov (United States)

    Kristoufek, Ladislav; Vosvrda, Miloslav

    2016-05-01

    Gold and currency markets form a unique pair with specific interactions and dynamics. We focus on the efficiency ranking of gold markets with respect to the currency of purchase. By utilizing the Efficiency Index (EI) based on fractal dimension, approximate entropy and long-term memory on a wide portfolio of 142 gold price series for different currencies, we construct the efficiency ranking based on the extended EI methodology we provide. Rather unexpected results are uncovered as the gold prices in major currencies lay among the least efficient ones whereas very minor currencies are among the most efficient ones. We argue that such counterintuitive results can be partly attributed to a unique period of examination (2011-2014) characteristic by quantitative easing and rather unorthodox monetary policies together with the investigated illegal collusion of major foreign exchange market participants, as well as some other factors discussed in some detail.

  2. Optical trapping of gold aerosols

    DEFF Research Database (Denmark)

    Schmitt, Regina K.; Pedersen, Liselotte Jauffred; Taheri, S. M.

    2015-01-01

    Aerosol trapping has proven challenging and was only recently demonstrated.1 This was accomplished by utilizing an air chamber designed to have a minimum of turbulence and a laser beam with a minimum of aberration. Individual gold nano-particles with diameters between 80 nm and 200 nm were trapped...... in air using a 1064 nm laser. The positions visited by the trapped gold nano-particle were quantified using a quadrant photo diode placed in the back focal plane. The time traces were analyzed and the trapping stiffness characterizing gold aerosol trapping determined and compared to aerosol trapping...... of nanometer sized silica and polystyrene particles. Based on our analysis, we concluded that gold nano-particles trap more strongly in air than similarly sized polystyrene and silica particles. We found that, in a certain power range, the trapping strength of polystyrene particles is linearly decreasing...

  3. Biomass processing over gold catalysts

    CERN Document Server

    Simakova, Olga A; Murzin, Dmitry Yu

    2014-01-01

    The book describes the valorization of biomass-derived compounds over gold catalysts. Since biomass is a rich renewable feedstock for diverse platform molecules, including those currently derived from petroleum, the interest in various transformation routes has become intense. Catalytic conversion of biomass is one of the main approaches to improving the economic viability of biorefineries.  In addition, Gold catalysts were found to have outstanding activity and selectivity in many key reactions. This book collects information about transformations of the most promising and important compounds derived from cellulose, hemicelluloses, and woody biomass extractives. Since gold catalysts possess high stability under oxidative conditions, selective oxidation reactions were discussed more thoroughly than other critical reactions such as partial hydrogenation, acetalization, and isomerization. The influence of reaction conditions, the role of the catalyst, and the advantages and disadvantages of using gold are pre...

  4. Structure relationship of cationic lipids on gene transfection mediated by cationic liposomes.

    Science.gov (United States)

    Paecharoenchai, Orapan; Niyomtham, Nattisa; Apirakaramwong, Auayporn; Ngawhirunpat, Tanasait; Rojanarata, Theerasak; Yingyongnarongkul, Boon-ek; Opanasopit, Praneet

    2012-12-01

    The aim of this study was to investigate the transfection efficiency of cationic liposomes formulated with phosphatidylcholine (PC) and novel synthesized diethanolamine-based cationic lipids at a molar ratio of 5:1 in comparison with Lipofectamine™ 2000. Factors affecting transfection efficiency and cell viability, including the chemical structure of the cationic lipids, such as different amine head group (diamine and polyamine; and non-spermine and spermine) and acyl chain lengths (C14, C16, and C18) and the weight ratio of liposomes to DNA were evaluated on a human cervical carcinoma cell line (HeLa cells) using the pDNA encoding green fluorescent protein (pEGFP-C2). Characterizations of these lipoplexes in terms of size and charge measurement and agarose gel electrophoresis were performed. The results from this study revealed that almost no transfection was observed in the liposome formulations composed of cationic lipids with a non-spermine head group. In addition, the transfection efficiency of these cationic liposomes was in the following order: spermine-C14 > spermine-C16 > spermine-C18. The highest transfection efficiency was observed in the formulation of spermine-C14 liposomes at a weight ratio of 25; furthermore, this formulation was safe for use in vitro. In conclusion, cationic liposomes containing spermine head groups demonstrated promising potential as gene carriers.

  5. Immunological properties of gold nanoparticles

    OpenAIRE

    Dykman, Lev A.; Khlebtsov, Nikolai G.

    2016-01-01

    In the past decade, gold nanoparticles have attracted strong interest from the nanobiotechnological community owing to the significant progress made in robust and easy-to-make synthesis technologies, in surface functionalization, and in promising biomedical applications. These include bioimaging, gene diagnostics, analytical sensing, photothermal treatment of tumors, and targeted delivery of various biomolecular and chemical cargos. For the last-named application, gold nanoparticles should be...

  6. Biosensors based on gold nanostructures

    OpenAIRE

    Vidotti,Marcio; Carvalhal,Rafaela F.; Mendes,Renata K.; Ferreira,Danielle C. M.; Kubota,Lauro T.

    2011-01-01

    The present review discusses the latest advances in biosensor technology achieved by the assembly of biomolecules associated with gold nanoparticles in analytical devices. This review is divided in sections according to the biomolecule employed in the biosensor development: (i) immunocompounds; (ii) DNA/RNA and functional DNA/RNA; and (iii) enzymes and Heme proteins. In order to facilitate the comprehension each section was subdivided according to the transduction mode. Gold nanoparticles bas...

  7. Characterisation of gold from Fiji

    OpenAIRE

    Naden, Jon; Henney, P.J.

    1995-01-01

    This is a study of the variation in chemistry and inclusion mineralogy of bedrock and placer gold from Fiji. It forms part of a large project, undertaking gold characterisation from a wide range of geological environments in Ecuador, Zimbabwe, Malaysia and Fiji. The work was carried out under the Overseas Development AdministratiodBritish Geological Survey Technology Development and Research programme (Project R5549) as part of the British Government’s provision of technical...

  8. Specifically colorimetric recognition of calcium, strontium, and barium ions using 2-mercaptosuccinic acid-functionalized gold nanoparticles and its use in reliable detection of calcium ion in water.

    Science.gov (United States)

    Zhang, Jia; Wang, Yong; Xu, Xiaowen; Yang, Xiurong

    2011-10-07

    A colorimetric probe based on 2-mercaptosuccinic acid-functionalized gold nanoparticles has been developed to exhibit selectivity towards Ca(2+), Sr(2+), and Ba(2+) ions over other metallic cations under specified conditions and finds its practical application in detecting Ca(2+) levels in water.

  9. Why can a gold salt react as a base?

    Science.gov (United States)

    Anania, Mariarosa; Jašíková, Lucie; Jašík, Juraj; Roithová, Jana

    2017-09-26

    This study shows that gold salts [(L)AuX] (L = PMe 3 , PPh 3 , JohnPhos, IPr; X = SbF 6 , PF 6 , BF 4 , TfO, Tf 2 N) act as bases in aqueous solutions and can transform acetone to digold acetonyl complexes [(L) 2 Au 2 (CH 2 COCH 3 )] + without any additional base present in solution. The key step is the formation of digold hydroxide complexes [(L) 2 Au 2 (OH)] + . The kinetics of the formation of the digold complexes and their mutual transformation is studied by electrospray ionization mass spectrometry and the delayed reactant labelling method. We show that the formation of digold hydroxide is the essential first step towards the formation of the digold acetonyl complex, the reaction is favoured by more polar solvents, and the effect of counter ions is negligible. DFT calculations suggest that digold hydroxide and digold acetonyl complexes can exist in solution only due to the stabilization by the interaction with two gold atoms. The reaction between the digold hydroxide and acetone proceeds towards the dimer {[(L)Au(OH)]·[(L)Au(CH 3 COCH 3 )] + }. The monomeric units interact at the gold atoms in the perpendicular arrangement typical of the gold clusters bound by the aurophilic interaction. The hydrogen is transferred within the dimer and the reaction continues towards the digold acetonyl complex and water.

  10. Fluconazole affects the alkali-metal-cation homeostasis and susceptibility to cationic toxic compounds of Candida glabrata.

    Science.gov (United States)

    Elicharova, Hana; Sychrova, Hana

    2014-08-01

    Candida glabrata is a salt-tolerant and fluconazole (FLC)-resistant yeast species. Here, we analyse the contribution of plasma-membrane alkali-metal-cation exporters, a cation/proton antiporter and a cation ATPase to cation homeostasis and the maintenance of membrane potential (ΔΨ). Using a series of single and double mutants lacking CNH1 and/or ENA1 genes we show that the inability to export potassium and toxic alkali-metal cations leads to a slight hyperpolarization of the plasma membrane of C. glabrata cells; this hyperpolarization drives more cations into the cells and affects cation homeostasis. Surprisingly, a much higher hyperpolarization of C. glabrata plasma membrane was produced by incubating cells with subinhibitory concentrations of FLC. FLC treatment resulted in a substantially increased sensitivity of cells to various cationic drugs and toxic cations that are driven into the cell by negative-inside plasma-membrane potential. The effect of the combination of FLC plus cationic drug treatment was enhanced by the malfunction of alkali-metal-cation transporters that contribute to the regulation of membrane potential and cation homeostasis. In summary, we show that the combination of subinhibitory concentrations of FLC and cationic drugs strongly affects the growth of C. glabrata cells. © 2014 The Authors.

  11. Synthesis, Structure, Stability and Redispersion of Gold-based Nanoparticles

    Science.gov (United States)

    Tiruvalam, Ram Chandra

    activated carbon and graphite substrates, with the exclusive formation of isolated gold atoms, dimeric species, and sub-nm clusters.

  12. Nuclear clustering - a cluster core model study

    International Nuclear Information System (INIS)

    Paul Selvi, G.; Nandhini, N.; Balasubramaniam, M.

    2015-01-01

    Nuclear clustering, similar to other clustering phenomenon in nature is a much warranted study, since it would help us in understanding the nature of binding of the nucleons inside the nucleus, closed shell behaviour when the system is highly deformed, dynamics and structure at extremes. Several models account for the clustering phenomenon of nuclei. We present in this work, a cluster core model study of nuclear clustering in light mass nuclei

  13. Comparative investigation on cation-cation (Al-Sn) and cation-anion (Al-F) co-doping in RF sputtered ZnO thin films: Mechanistic insight

    Energy Technology Data Exchange (ETDEWEB)

    Mallick, Arindam; Basak, Durga, E-mail: sspdb@iacs.res.in

    2017-07-15

    Highlights: • Comparative study on Al, Al-Sn and Al-F doped ZnO films has been carried out. • High transparent Al-F co-doped film shows three times enhanced carrier density. • Al-F co-doped film shows larger carrier relaxation time. • Al-Sn co-doped films shows carrier transport dominated by impurity scattering. • Al-F co-doped ZnO film can be applied as transparent electrode. - Abstract: Herein, we report a comparative mechanistic study on cation-cation (Al-Sn) and cation-anion (Al-F) co-doped nanocrystalline ZnO thin films grown on glass substrate by RF sputtering technique. Through detailed analyses of crystal structure, surface morphology, microstructure, UV-VIS-NIR transmission-reflection and electrical transport property, the inherent characteristics of the co-doped films were revealed and compared. All the nanocrystalline films retain the hexagonal wurtzite structure of ZnO and show transparency above 90% in the visible and NIR region. As opposed to expectation, Al-Sn (ATZO) co-doped film show no enhanced carrier concentration consistent with the probable formation of SnO{sub 2} clusters supported by the X-ray photoelectron spectroscopy study. Most interestingly, it has been found that Al-F (AFZO) co-doped film shows three times enhanced carrier concentration as compared to Al doped and Al-Sn co-doped films attaining a value of ∼9 × 10{sup 20} cm{sup −3} due to the respective cation and anion substitution. The carrier relaxation time increases in AFZO while it decreases significantly for ATZO film consistent with the concurrence of the impurity scattering in the latter.

  14. (4 + 3) Cycloadditions of Nitrogen-Stabilized Oxyallyl Cations

    Science.gov (United States)

    Lohse, Andrew G.; Hsung, Richard P.

    2011-01-01

    The use of heteroatom-substituted oxyallyl cations in (4 + 3) cycloadditions has had a tremendous impact on the development of cycloaddition chemistry. Extensive efforts have been exerted toward investigating the effect of oxygen-, sulfur-, and halogen-substituents on the reactivity of oxyallyl cations. Most recently, the use of nitrogen-stabilized oxyallyl cations has gained prominence in the area of (4 + 3) cycloadditions. The following article will provide an overview of this concept utilizing nitrogen-stabilized oxyallyl cations. PMID:21384451

  15. Selective alkylation by photogenerated aryl and vinyl cation

    NARCIS (Netherlands)

    Slegt, Micha

    2006-01-01

    Seven para-substituted phenyl cations and the parent phenyl cation were prepared from iodonium salt precursors. Product studies revealed remarkable chemoselectivity and regioselectivity that could be related to the spin multiplicity of the cations. Also an universal method to fingerprint singlet and

  16. Titanium embedded cage structure formation in AlnTi+ clusters and their interaction with Ar

    International Nuclear Information System (INIS)

    Torres, M. B.; Vega, A.; Balbás, L. C.; Aguilera-Granja, F.

    2014-01-01

    Recently, Ar physisorption was used as a structural probe for the location of the Ti dopant atom in aluminium cluster cations, Al n Ti + [Lang et al., J. Am. Soc. Mass Spectrom. 22, 1508 (2011)]. As an experiment result, the lack of Ar complexes for n > n c determines the cluster size for which the Ti atom is located inside of an Al cage. To elucidate the decisive factors for the formation of endohedrally Al n Ti + , experimentalists proposed detailed computational studies as indispensable. In this work, we investigated, using the density functional theory, the structural and electronic properties of singly titanium doped cationic clusters, Al n Ti + (n = 16–21) as well as the adsorption of an Ar atom on them. The first endohedral doped cluster, with Ti encapsulated in a fcc-like cage skeleton, appears at n c = 21, which is the critical number consistent with the exohedral-endohedral transition experimentally observed. At this critical size the non-crystalline icosahedral growth pattern, related to the pure aluminium clusters, with the Ti atom in the surface, changes into a endohedral fcc-like pattern. The map of structural isomers, relative energy differences, second energy differences, and structural parameters were determined and analyzed. Moreover, we show the critical size depends on the net charge of the cluster, being different for the cationic clusters (n c = 21) and their neutral counterparts (n c = 20). For the Al n Ti + · Ar complexes, and for n n Ti + clusters keeps unaltered in the Ar-cluster complexes. This fact indicates that Ar adsorption does not influence the cluster structure, providing support to the experimental technique used. For n c = 21, the smallest size of endohedral Ti doped cationic clusters, the Ar binding energy decreases drastically, whereas the Ar-cluster distance increases substantially, point to Ar physisorption, as assumed by the experimentalists. Calculated Ar adsorption energies agree well with available experimental binding

  17. Gold nanoparticles for cancer detection and treatment: The role of adhesion

    International Nuclear Information System (INIS)

    Oni, Y.; Hao, K.; Dozie-Nwachukwu, S.; Odusanya, O. S.; Obayemi, J.D.; Anuku, N.; Soboyejo, W. O.

    2014-01-01

    This paper presents the results of an experimental study of the effects of adhesion between gold nanoparticles and surfaces that are relevant to the potential applications in cancer detection and treatment. Adhesion is measured using a dip coating/atomic force microscopy (DC/AFM) technique. The adhesion forces are obtained for dip-coated gold nanoparticles that interact with peptide or antibody-based molecular recognition units (MRUs) that attach specifically to breast cancer cells. They include MRUs that attach specifically to receptors on breast cancer cells. Adhesion forces between anti-cancer drugs such as paclitaxel, and the constituents of MRU-conjugated Au nanoparticle clusters, are measured using force microscopy techniques. The implications of the results are then discussed for the design of robust gold nanoparticle clusters and for potential applications in localized drug delivery and hyperthermia

  18. Catalytic enhancement of gold nanocages induced by undercoordination-charge-polarization

    Directory of Open Access Journals (Sweden)

    Xi Zhang

    2017-05-01

    Full Text Available Principle behind the highest catalytic ability of the least coordinated gold remains a puzzle. With the aid of density functional theory calculations, we show that in 3-coordinated gold cages (i the Au–Au bond contracts by ∼5% in average, (ii the valance density-of-states shift up to Fermi level when the Au55 cluster turns into an Au12 cage, and (iii the activation energy for CO oxidation drops in sequence, Au55 cluster (13.6 Kcal/mol, Au42 cage (8.0 Kcal/mol, Au13(6.5 Kcal/mol, and Au12 cage (5.1 Kcal/mol, with comparing the reaction paths and spin states. The principle clarified here paves the way for the design of gold nanocatalyst.

  19. Gold nanoparticles for cancer detection and treatment: The role of adhesion

    Energy Technology Data Exchange (ETDEWEB)

    Oni, Y. [Princeton Institute for Science and Technology of Materials (PRISM), Princeton University, 70 Prospect Street, Princeton, New Jersey 08544 (United States); Department of Mechanical and Aerospace Engineering, Princeton University, Princeton, New Jersey 08544 (United States); Hao, K. [Department of Civil and Environmental Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 (United States); Dozie-Nwachukwu, S.; Odusanya, O. S. [African University of Science and Technology (AUST), Kilometer 10, Airport Road, Abuja, Federal Capital Territory (Nigeria); Sheda Science and Technology Complex (SHESTCO), Gwagwalada, Abuja, Federal Capital Territory (Nigeria); Obayemi, J.D. [African University of Science and Technology (AUST), Kilometer 10, Airport Road, Abuja, Federal Capital Territory (Nigeria); Anuku, N. [Department of Mechanical and Aerospace Engineering, Princeton University, Princeton, New Jersey 08544 (United States); Department of Chemistry and Chemical Technology, Bronx Community College, New York, New York 10453 (United States); Soboyejo, W. O. [Princeton Institute for Science and Technology of Materials (PRISM), Princeton University, 70 Prospect Street, Princeton, New Jersey 08544 (United States); Department of Mechanical and Aerospace Engineering, Princeton University, Princeton, New Jersey 08544 (United States); African University of Science and Technology (AUST), Kilometer 10, Airport Road, Abuja, Federal Capital Territory (Nigeria)

    2014-02-28

    This paper presents the results of an experimental study of the effects of adhesion between gold nanoparticles and surfaces that are relevant to the potential applications in cancer detection and treatment. Adhesion is measured using a dip coating/atomic force microscopy (DC/AFM) technique. The adhesion forces are obtained for dip-coated gold nanoparticles that interact with peptide or antibody-based molecular recognition units (MRUs) that attach specifically to breast cancer cells. They include MRUs that attach specifically to receptors on breast cancer cells. Adhesion forces between anti-cancer drugs such as paclitaxel, and the constituents of MRU-conjugated Au nanoparticle clusters, are measured using force microscopy techniques. The implications of the results are then discussed for the design of robust gold nanoparticle clusters and for potential applications in localized drug delivery and hyperthermia.

  20. An interpretation of the absorption and emission spectra of the gold dimer using modern theoretical tools

    DEFF Research Database (Denmark)

    Geethalakshmi, K. R.; Ruiperez, F.; Knecht, S.

    2012-01-01

    The excited states of the gold dimer have been investigated using modern theoretical tools including the multiconfigurational exact molecular mean-field intermediate Hamiltonian Fock-space Coupled Cluster, X2Cmmf-IHFSCC, and the complete active space self-consistent field followed by second order...

  1. An interpretation of the absorption and emission spectra of the gold dimer using modern theoretical tools

    NARCIS (Netherlands)

    Geethalakshmi, K R; Ruipérez, Fernando; Knecht, Stefan; Ugalde, Jesus M.; Morse, Michael D.; Infante, Ivan

    2012-01-01

    The excited states of the gold dimer have been investigated using modern theoretical tools including the multiconfigurational exact molecular mean-field intermediate Hamiltonian Fock-space Coupled Cluster, X2Cmmf-IHFSCC, and the complete active space self-consistent field followed by second order

  2. Radiation chemistry of aromatic dimer radical cations

    International Nuclear Information System (INIS)

    Okamoto, Kazumasa; Tagawa, Seiichi

    2009-01-01

    π-π Interactions of aromatic molecules are paid attention much in many fields, especially biology, chemistry, and applied physics, represented as protein, DNA, electron donor-accepter complexes, charge transfers, and self assembly molecules. Aromatic molecules including benzene rings are the simplest case to study the π-π interactions. To interpret the charge resonance (CR) structure in the dimer radical cations, spectroscopic and ESR methods have been carried out. The spectroscopic study on the dimer radical ion of molecules with two chromophores would be profitable to identify the electronic and configurational properties. In this article, dynamics of the dimer radical cation of benzenes, polystyrenes, and resist polymers is described on the basis of direct observation of CR band by the nanosecond pulse radiolysis and low temperature γ-radiolysis methods. (author)

  3. Electronic spectrum of 9-methylanthracenium radical cation

    Energy Technology Data Exchange (ETDEWEB)

    O’Connor, Gerard D.; Schmidt, Timothy W., E-mail: timothy.schmidt@unsw.edu.au [School of Chemistry, UNSW Sydney, New South Wales 2052 (Australia); Sanelli, Julian A.; Dryza, Vik; Bieske, Evan J. [School of Chemistry, The University of Melbourne, Victoria 3010 (Australia)

    2016-04-21

    The predissociation spectrum of the cold, argon-tagged, 9-methylanthracenium radical cation is reported from 8000 cm{sup −1} to 44 500 cm{sup −1}. The reported spectrum contains bands corresponding to at least eight electronic transitions ranging from the near infrared to the ultraviolet. These electronic transitions are assigned through comparison with ab initio energies and intensities. The infrared D{sub 1}←D{sub 0} transitions exhibit significant vibronic activity, which is assigned through comparison with TD-B3LYP excited state frequencies and intensities, as well as modelled vibronic interactions. Dissociation of 9-methylanthracenium is also observed at high visible-photon energies, resulting in the loss of either CH{sub 2} or CH{sub 3}. The relevance of these spectra, and the spectra of other polycyclic aromatic hydrocarbon radical cations, to the largely unassigned diffuse interstellar bands, is discussed.

  4. Photodissociation of spatially aligned acetaldehyde cations.

    Science.gov (United States)

    Lee, Suk Kyoung; Silva, Ruchira; Kim, Myung Hwa; Shen, Lei; Suits, Arthur G

    2007-07-26

    Photofragment translational energy and angular distributions are reported for the photodissociation of acetaldehyde cations in the wavelength range 354-363 nm obtained using the DC slice ion imaging technique. Vibrationally selected parent ions were produced by 2+1 resonance-enhanced multiphoton ionization (REMPI) via the 3sCH3CO+, and CH4+. The angular distributions reveal that all product channels have a predominantly parallel recoil anisotropy although the lower beta2 parameter of CH3CO+ indicates the concomitant presence of a perpendicular component. Furthermore, the distinct angular distribution of the CH3CO+ fragments shows a large value of the higher order Legendre polynomial term, providing evidence that acetaldehyde cations are spatially aligned during the ionization process.

  5. Mechanism of adsorption of cations onto rocks

    International Nuclear Information System (INIS)

    Kitamura, Akira; Yamamoto, Tadashi; Fujiwara, Kenso; Nishikawa, Sataro; Moriyama, Hirotake

    1999-01-01

    Adsorption behavior of cations onto granite was investigated. The distribution coefficient (K d ) of Sr 2+ and Ba 2+ onto granite was determined in the solution of which pH was ranged from 3.5 to 11.3 and ionic strength was set at 10 -2 and 10 -1 . The K d values were found to increase with increasing pH and with deceasing ionic strength. The obtained data were successfully analyzed by applying an electrical double layer model. The optimum parameter values of the double layer electrostatics and adsorption reactions were obtained, and the mechanism of adsorption of cations onto granite was discussed. Feldspar was found to play an important role in their adsorption. (author)

  6. Straightforward and robust synthesis of monodisperse surface-functionalized gold nanoclusters

    Directory of Open Access Journals (Sweden)

    Silvia Varela-Aramburu

    2016-09-01

    Full Text Available Gold nanoclusters are small (1–3 nm nanoparticles with a high surface area that are useful for biomedical studies and drug delivery. The synthesis of small, surface-functionalized gold nanoclusters is greatly dependent on the reaction conditions. Here, we describe a straightforward, efficient and robust room temperature one-pot synthesis of 2 nm gold nanoclusters using thioglucose as a reducing and stabilizing agent, which was discovered by serendipity. The resultant monodisperse gold nanoclusters are more stable than those generated using some other common methods. The carboxylic acid contained in the stabilizing agent on the cluster surface serves as anchor for nanocluster functionalization. Alternatively, the addition of thiols serves to functionalize the nanoclusters. The resulting non-cytotoxic nanoclusters are taken up by cells and constitute a tuneable platform for biomedical applications including drug delivery.

  7. Regulation of Cation Balance in Saccharomyces cerevisiae

    Science.gov (United States)

    Cyert, Martha S.; Philpott, Caroline C.

    2013-01-01

    All living organisms require nutrient minerals for growth and have developed mechanisms to acquire, utilize, and store nutrient minerals effectively. In the aqueous cellular environment, these elements exist as charged ions that, together with protons and hydroxide ions, facilitate biochemical reactions and establish the electrochemical gradients across membranes that drive cellular processes such as transport and ATP synthesis. Metal ions serve as essential enzyme cofactors and perform both structural and signaling roles within cells. However, because these ions can also be toxic, cells have developed sophisticated homeostatic mechanisms to regulate their levels and avoid toxicity. Studies in Saccharomyces cerevisiae have characterized many of the gene products and processes responsible for acquiring, utilizing, storing, and regulating levels of these ions. Findings in this model organism have often allowed the corresponding machinery in humans to be identified and have provided insights into diseases that result from defects in ion homeostasis. This review summarizes our current understanding of how cation balance is achieved and modulated in baker’s yeast. Control of intracellular pH is discussed, as well as uptake, storage, and efflux mechanisms for the alkali metal cations, Na+ and K+, the divalent cations, Ca2+ and Mg2+, and the trace metal ions, Fe2+, Zn2+, Cu2+, and Mn2+. Signal transduction pathways that are regulated by pH and Ca2+ are reviewed, as well as the mechanisms that allow cells to maintain appropriate intracellular cation concentrations when challenged by extreme conditions, i.e., either limited availability or toxic levels in the environment. PMID:23463800

  8. Reducible cationic lipids for gene transfer.

    Science.gov (United States)

    Wetzer, B; Byk, G; Frederic, M; Airiau, M; Blanche, F; Pitard, B; Scherman, D

    2001-01-01

    One of the main challenges of gene therapy remains the increase of gene delivery into eukaryotic cells. We tested whether intracellular DNA release, an essential step for gene transfer, could be facilitated by using reducible cationic DNA-delivery vectors. For this purpose, plasmid DNA was complexed with cationic lipids bearing a disulphide bond. This reduction-sensitive linker is expected to be reduced and cleaved in the reducing milieu of the cytoplasm, thus potentially improving DNA release and consequently transfection. The DNA--disulphide-lipid complexation was monitored by ethidium bromide exclusion, and the size of complexes was determined by dynamic light scattering. It was found that the reduction kinetics of disulphide groups in DNA--lipid complexes depended on the position of the disulphide linker within the lipid molecule. Furthermore, the internal structure of DNA--lipid particles was examined by small-angle X-ray scattering before and after lipid reduction. DNA release from lipid complexes was observed after the reduction of disulphide bonds of several lipids. Cell-transfection experiments suggested that complexes formed with selected reducible lipids resulted in up to 1000-fold higher reporter-gene activity, when compared with their analogues without disulphide bonds. In conclusion, reduction-sensitive groups introduced into cationic lipid backbones potentially allow enhanced DNA release from DNA--lipid complexes after intracellular reduction and represent a tool for improved vectorization. PMID:11389682

  9. Increased localized delivery of piroxicam by cationic nanoparticles after intra-articular injection.

    Science.gov (United States)

    Kim, Sung Rae; Ho, Myoung Jin; Kim, Sang Hyun; Cho, Ha Ra; Kim, Han Sol; Choi, Yong Seok; Choi, Young Wook; Kang, Myung Joo

    2016-01-01

    Piroxicam (PRX), a potent nonsteroidal anti-inflammatory drug, is prescribed to relieve postoperative and/or chronic joint pain. However, its oral administration often results in serious gastrointestinal adverse effects including duodenal ulceration. Thus, a novel cationic nanoparticle (NP) was explored to minimize the systemic exposure and increase the retention time of PRX in the joint after intra-articular (IA) injection, by forming micrometer-sized electrostatic clusters with endogenous hyaluronic acid (HA) in the synovial cavity. PRX-loaded NPs consisting of poly(lactic- co -glycolic acid), Eudragit RL, and polyvinyl alcohol were constructed with the following characteristics: particle size of 220 nm, zeta potential of 11.5 mV in phosphate-buffered saline, and loading amount of 4.0% (w/w) of PRX. In optical and hyperspectral observations, the cationic NPs formed more than 50 μm-sized aggregates with HA, which was larger than the intercellular gaps between synoviocytes. In an in vivo pharmacokinetic study in rats, area under the plasma concentration-time curve (AUC 0-24 h ) and maximum plasma concentration ( C max ) of PRX after IA injection of the cationic NPs were <70% ( P <0.05) and 60% ( P <0.05), respectively, compared to those obtained from drug solution. Moreover, the drug concentration in joint tissue 24 h after dosing with the cationic NPs was 3.2-fold ( P <0.05) and 1.8-fold ( P <0.05) higher than that from drug solution and neutrally charged NPs, respectively. Therefore, we recommend the IA cationic NP therapy as an effective alternative to traditional oral therapy with PRX, as it increases drug retention selectively in the joint.

  10. Cluster headache

    Directory of Open Access Journals (Sweden)

    Ducros Anne

    2008-07-01

    Full Text Available Abstract Cluster headache (CH is a primary headache disease characterized by recurrent short-lasting attacks (15 to 180 minutes of excruciating unilateral periorbital pain accompanied by ipsilateral autonomic signs (lacrimation, nasal congestion, ptosis, miosis, lid edema, redness of the eye. It affects young adults, predominantly males. Prevalence is estimated at 0.5–1.0/1,000. CH has a circannual and circadian periodicity, attacks being clustered (hence the name in bouts that can occur during specific months of the year. Alcohol is the only dietary trigger of CH, strong odors (mainly solvents and cigarette smoke and napping may also trigger CH attacks. During bouts, attacks may happen at precise hours, especially during the night. During the attacks, patients tend to be restless. CH may be episodic or chronic, depending on the presence of remission periods. CH is associated with trigeminovascular activation and neuroendocrine and vegetative disturbances, however, the precise cautive mechanisms remain unknown. Involvement of the hypothalamus (a structure regulating endocrine function and sleep-wake rhythms has been confirmed, explaining, at least in part, the cyclic aspects of CH. The disease is familial in about 10% of cases. Genetic factors play a role in CH susceptibility, and a causative role has been suggested for the hypocretin receptor gene. Diagnosis is clinical. Differential diagnoses include other primary headache diseases such as migraine, paroxysmal hemicrania and SUNCT syndrome. At present, there is no curative treatment. There are efficient treatments to shorten the painful attacks (acute treatments and to reduce the number of daily attacks (prophylactic treatments. Acute treatment is based on subcutaneous administration of sumatriptan and high-flow oxygen. Verapamil, lithium, methysergide, prednisone, greater occipital nerve blocks and topiramate may be used for prophylaxis. In refractory cases, deep-brain stimulation of the

  11. Anchoring cationic amphiphiles for nucleotide delivery: significance of DNA release from cationic liposomes for transfection.

    Science.gov (United States)

    Hirashima, Naohide; Minatani, Kazuhiro; Hattori, Yoshifumi; Ohwada, Tomohiko; Nakanishi, Mamoru

    2007-06-01

    We have designed and synthesized lithocholic acid-based cationic amphiphile molecules as components of cationic liposomes for gene transfection (lipofection). To study the relationship between the molecular structures of those amphiphilic molecules, particularly the extended hydrophobic appendant (anchor) at the 3-hydroxyl group, and transfection efficiency, we synthesized several lithocholic and isolithocholic acid derivatives, and examined their transfection efficiency. We also compared the physico-chemical properties of cationic liposomes prepared from these derivatives. We found that isolithocholic acid derivatives exhibit higher transfection efficiency than the corresponding lithocholic acid derivatives. This result indicates that the orientation and extension of hydrophobic regions influence the gene transfection process. Isolithocholic acid derivatives showed a high ability to encapsulate DNA in a compact liposome-DNA complex and to protect it from enzymatic degradation. Isolithocholic acid derivatives also facilitated the release of DNA from the liposome-DNA complex, which is a crucial step for DNA entry into the nucleus. Our results show that the transfection efficiency is directly influenced by the ability of the liposome complex to release DNA, rather than by the DNA-encapsulating ability. Molecular modeling revealed that isolithocholic acid derivatives take relatively extended conformations, while the lithocholic acid derivatives take folded structures. Thus, the efficiency of release of DNA from cationic liposomes in the cytoplasm, which contributes to high transfection efficiency, appears to be dependent upon the molecular shape of the cationic amphiphiles.

  12. Comparative analysis of cation/proton antiporter superfamily in plants.

    Science.gov (United States)

    Ye, Chu-Yu; Yang, Xiaohan; Xia, Xinli; Yin, Weilun

    2013-06-01

    The cation/proton antiporter superfamily is associated with the transport of monovalent cations across membranes. This superfamily was annotated in the Arabidopsis genome and some members were functionally characterized. In the present study, a systematic analysis of the cation/proton antiporter genes in diverse plant species was reported. We identified 240 cation/proton antiporters in alga, moss, and angiosperm. A phylogenetic tree was constructed showing these 240 members are separated into three families, i.e., Na(+)/H(+) exchangers, K(+) efflux antiporters, and cation/H(+) exchangers. Our analysis revealed that tandem and/or segmental duplications contribute to the expansion of cation/H(+) exchangers in the examined angiosperm species. Sliding window analysis of the nonsynonymous/synonymous substitution ratios showed some differences in the evolutionary fate of cation/proton antiporter paralogs. Furthermore, we identified over-represented motifs among these 240 proteins and found most motifs are family specific, demonstrating diverse evolution of the cation/proton antiporters among three families. In addition, we investigated the co-expressed genes of the cation/proton antiporters in Arabidopsis thaliana. The results showed some biological processes are enriched in the co-expressed genes, suggesting the cation/proton antiporters may be involved in these biological processes. Taken together, this study furthers our knowledge on cation/proton antiporters in plants. Copyright © 2013 Elsevier B.V. All rights reserved.

  13. Glucose oxidase-functionalized fluorescent gold nanoclusters as probes for glucose

    Energy Technology Data Exchange (ETDEWEB)

    Xia, Xiaodong [College of Chemistry and Chemical Engineering, Central South University, Changsha 410083 (China); School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan 411201 (China); Long, Yunfei, E-mail: l_yunfei927@163.com [School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan 411201 (China); Wang, Jianxiu, E-mail: jxiuwang@csu.edu.cn [College of Chemistry and Chemical Engineering, Central South University, Changsha 410083 (China)

    2013-04-15

    Highlights: ► A glucose oxidase/gold nanocluster conjugates formed by etching chemistry. ► Integration of the bioactivities and fluorescence properties within a single unit. ► These conjugates serve as novel fluorescent probe for glucose. -- Abstract: Creation and application of noble metal nanoclusters have received continuous attention. By integrating enzyme activity and fluorescence for potential applications, enzyme-capped metal clusters are more desirable. This work demonstrated a glucose oxidase (an enzyme for glucose)-functionalized gold cluster as probe for glucose. Under physiological conditions, such bioconjugate was successfully prepared by an etching reaction, where tetrakis (hydroxylmethyl) phosphonium-protected gold nanoparticle and thioctic acid-modified glucose oxidase were used as precursor and etchant, respectively. These bioconjugates showed unique fluorescence spectra (λ{sub em} {sub max} = 650 nm, λ{sub ex} {sub max} = 507 nm) with an acceptable quantum yield (ca. 7%). Moreover, the conjugated glucose oxidase remained active and catalyzed reaction of glucose and dissolved O{sub 2} to produce H{sub 2}O{sub 2}, which quenched quantitatively the fluorescence of gold clusters and laid a foundation of glucose detection. A linear range of 2.0 × 10{sup −6}–140 × 10{sup −6} M and a detection limit of 0.7 × 10{sup −6} M (S/N = 3) were obtained. Also, another horseradish peroxidase/gold cluster bioconjugate was produced by such general synthesis method. Such enzyme/metal cluster bioconjugates represented a promising class of biosensors for biologically important targets in organelles or cells.

  14. Annealing relaxation of ultrasmall gold nanostructures

    Science.gov (United States)

    Chaban, Vitaly

    2015-01-01

    Except serving as an excellent gift on proper occasions, gold finds applications in life sciences, particularly in diagnostics and therapeutics. These applications were made possible by gold nanoparticles, which differ drastically from macroscopic gold. Versatile surface chemistry of gold nanoparticles allows coating with small molecules, polymers, biological recognition molecules. Theoretical investigation of nanoscale gold is not trivial, because of numerous metastable states in these systems. Unlike elsewhere, this work obtains equilibrium structures using annealing simulations within the recently introduced PM7-MD method. Geometries of the ultrasmall gold nanostructures with chalcogen coverage are described at finite temperature, for the first time.

  15. Phage based green chemistry for gold ion reduction and gold retrieval.

    Science.gov (United States)

    Setyawati, Magdiel I; Xie, Jianping; Leong, David T

    2014-01-22

    The gold mining industry has taken its toll on the environment, triggering the development of more environmentally benign processes to alleviate the waste load release. Here, we demonstrate the use of bacteriophages (phages) for biosorption and bioreduction of gold ions from aqueous solution, which potentially can be applied to remediate gold ions from gold mining waste effluent. Phage has shown a remarkably efficient sorption of gold ions with a maximum gold adsorption capacity of 571 mg gold/g dry weight phage. The product of this phage mediated process is gold nanocrystals with the size of 30-630 nm. Biosorption and bioreduction processes are mediated by the ionic and covalent interaction between gold ions and the reducing groups on the phage protein coat. The strategy offers a simple, ecofriendly and feasible option to recover of gold ions to form readily recoverable products of gold nanoparticles within 24 h.

  16. Brightest Cluster Galaxies in REXCESS Clusters

    Science.gov (United States)

    Haarsma, Deborah B.; Leisman, L.; Bruch, S.; Donahue, M.

    2009-01-01

    Most galaxy clusters contain a Brightest Cluster Galaxy (BCG) which is larger than the other cluster ellipticals and has a more extended profile. In the hierarchical model, the BCG forms through many galaxy mergers in the crowded center of the cluster, and thus its properties give insight into the assembly of the cluster as a whole. In this project, we are working with the Representative XMM-Newton Cluster Structure Survey (REXCESS) team (Boehringer et al 2007) to study BCGs in 33 X-ray luminous galaxy clusters, 0.055 < z < 0.183. We are imaging the BCGs in R band at the Southern Observatory for Astrophysical Research (SOAR) in Chile. In this poster, we discuss our methods and give preliminary measurements of the BCG magnitudes, morphology, and stellar mass. We compare these BCG properties with the properties of their host clusters, particularly of the X-ray emitting gas.

  17. Radical cations of quadricyclane and norbornadiene in polar ZSM-5 matrices: Radical cation photochemical transformations without photons

    International Nuclear Information System (INIS)

    Barnabas, M.V.; Trifunac, A.D.

    1994-01-01

    Radical cations of quadricyclane (Q) and norbornadiene (NBD) are produced by γ-radiolysis in zeolites. In polar ZSM-5, only one radical cation is initially observed below 100K. Increasing the temperature above 200K gives rise to the cyclopentadiene radical cation. Higher temperatures (>360K) give rise to the cyclopenten-4-yl radical. The observation of cyclopentadiene radical cation implies the occurrence of the reverse Diels-Alder reaction. This is a thermally forbidden, photochemically allowed, process, which is made possible by the interaction of the polar zeolite matrix sites with parent NBD and Q radical cations

  18. Incorporation of a Cationic Conjugated Polyelectrolyte CPE within an Aqueous Poly(vinyl alcohol) Sol

    DEFF Research Database (Denmark)

    Knaapila, Matti; Stewart, Beverly; Costa, Telma

    2016-01-01

    We report on a multiscale polymer-within-polymer structure of the cationic conjugated polyelectrolyte poly{[9,9-bis(6-N,N,N-trimethylammonium)hexyl]fluorene phenylene} (HTMAPFP) in aqueous poly(vinyl alcohol).(PVA) sol. Molecular dynamics simulations and small-angle neutron scattering (SANS) data...... show that HTMA-PFP forms aggregates in water but becomes entangled by PVA (with a 1:1 molar ratio of HTMA-PFP to PVA) and eventually immersed in PVA clusters (with the ratio 1:4). This is attributed to the hydrophobic hydrophilic balance. Contrast variation data with regular and deuterated PVA support...

  19. Partitional clustering algorithms

    CERN Document Server

    2015-01-01

    This book summarizes the state-of-the-art in partitional clustering. Clustering, the unsupervised classification of patterns into groups, is one of the most important tasks in exploratory data analysis. Primary goals of clustering include gaining insight into, classifying, and compressing data. Clustering has a long and rich history that spans a variety of scientific disciplines including anthropology, biology, medicine, psychology, statistics, mathematics, engineering, and computer science. As a result, numerous clustering algorithms have been proposed since the early 1950s. Among these algorithms, partitional (nonhierarchical) ones have found many applications, especially in engineering and computer science. This book provides coverage of consensus clustering, constrained clustering, large scale and/or high dimensional clustering, cluster validity, cluster visualization, and applications of clustering. Examines clustering as it applies to large and/or high-dimensional data sets commonly encountered in reali...

  20. Nano-jewellery: C5Au12--a gold-plated diamond at molecular level.

    Science.gov (United States)

    Naumkin, F

    2006-06-07

    A mixed carbon-metal cluster is designed by combining the tetrahedral C(5) radical (with a central atom-the skeleton of the C(5)H(12) molecule) and the spherical Au(12) layer (the external atomic shell of the Au(13) cluster). The C(5)Au(12) cluster and its negative and positive ionic derivatives, C(5)Au(12)(+/-), are investigated ab initio (DFT) in terms of optimized structures and relative energies of a few spin-states, for the icosahedral-like and octahedral-like isomers. The cluster is predicted to be generally more stable in its octahedral shape (similar to C(5)H(12)) which prevails for the negative ion and may compete with the icosahedral shape for the neutral system and positive ion. Adiabatic ionization energies (AIE) and electron affinities (AEA) of C(5)Au(12), vertical electron-detachment (VDE) energies of C(5)Au(12)(-), and vertical ionization and electron-attachment energies (VIE, VEA) of C(5)Au(12) are calculated as well, and compared with those for the corresponding isomers of the Au(13) cluster. The AIE and VIE values are found to be close for the two systems, while the AEA and VDE values are significantly reduced for the radical-based species. A simple fragment-based model is proposed for the decomposition of the total interaction into carbon-gold and gold-gold components.

  1. Gold nanoparticles stabilized by chitosan

    International Nuclear Information System (INIS)

    Geraldes, Adriana N.; Oliveira, Maria Jose A.; Silva, Andressa A. da; Leal, Jessica; Batista, Jorge G.S.; Lugao, Ademar B.

    2015-01-01

    In our laboratory has been growing the interest in studying gold nanoparticles and for this reason, the aim of this work is report the first results of the effect of chitosan as stabilizer in gold nanoparticle formulation. AuNPs were synthesized by reducing hydrogen tetrachloroaurate (HAuCl 4 ) using NaBH 4 or gamma irradiation (25kGy) as reduction agent. The chitosan (3 mol L -1 ) was added at 0.5; 1.0 and 1.5 mL. The gold nanoparticles were characterized by UV-Vis absorption spectroscopy, X-ray diffraction (XRD) and Transmission electron microscopy (TEM). Their physical stability was determined using a UV-Vis spectrophotometer over one week during storage at room temperature. Absorption measurements indicated that the plasmon resonance wavelength appears at a wavelength around 530 nm. Has been observed that Chitosan in such quantities were not effective in stabilizing the AuNPs. (author)

  2. Cationic niosomes an effective gene carrier composed of novel spermine-derivative cationic lipids: effect of central core structures.

    Science.gov (United States)

    Opanasopit, Praneet; Leksantikul, Lalita; Niyomtham, Nattisa; Rojanarata, Theerasak; Ngawhirunpat, Tanasait; Yingyongnarongkul, Boon-Ek

    2017-05-01

    Cationic niosomes formulated from Span 20, cholesterol (Chol) and novel spermine-based cationic lipids of multiple central core structures (di(oxyethyl)amino, di(oxyethyl)amino carboxy, 3-amino-1,2-dioxypropyl and 2-amino-1,3-dioxypropyl) were successfully prepared for improving transfection efficiency in vitro. The niosomes composed of spermine cationic lipid with central core structure of di(oxyethyl)amino revealed the highest gene transfection efficiency. To investigate the factors affecting gene transfection and cell viability including differences in the central core structures of cationic lipids, the composition of vesicles, molar ratio of cationic lipids in formulations and the weight ratio of niosomes to DNA. Cationic niosomes composed of nonionic surfactants (Span20), cholesterol and spermine-based cationic lipids of multiple central core structures were formulated. Gene transfection and cell viability were evaluated on a human cervical carcinoma cell line (HeLa cells) using pDNA encoding green fluorescent protein (pEGFP-C2). The morphology, size and charge were also characterized. High transfection efficiency was obtained from cationic niosomes composed of Span20:Chol:cationic lipid at the molar ratio of 2.5:2.5:0.5 mM. Cationic lipids with di(oxyethyl)amino as a central core structure exhibited highest transfection efficiency. In addition, there was also no serum effect on transfection efficiency. These novel cationic niosomes may constitute a good alternative carrier for gene transfection.

  3. Plasmonic Horizon in Gold Nanosponges.

    Science.gov (United States)

    Vidal, Cynthia; Sivun, Dmitry; Ziegler, Johannes; Wang, Dong; Schaaf, Peter; Hrelescu, Calin; Klar, Thomas A

    2018-02-14

    An electromagnetic wave impinging on a gold nanosponge coherently excites many electromagnetic hot-spots inside the nanosponge, yielding a polarization-dependent scattering spectrum. In contrast, a hole, recombining with an electron, can locally excite plasmonic hot-spots only within a horizon given by the lifetime of localized plasmons and the speed carrying the information that a plasmon has been created. This horizon is about 57 nm, decreasing with increasing size of the nanosponge. Consequently, photoluminescence from large gold nanosponges appears unpolarized.

  4. A Novel Strategy for Synthesis of Gold Nanoparticle Self Assemblies

    NARCIS (Netherlands)

    Verma, Jyoti; Lal, Sumit; van Veen, Henk A.; van Noorden, Cornelis J. F.

    2014-01-01

    Gold nanoparticle self assemblies are one-dimensional structures of gold nanoparticles. Gold nanoparticle self assemblies exhibit unique physical properties and find applications in the development of biosensors. Methodologies currently available for lab-scale and commercial synthesis of gold

  5. Electron-Poor Polar Intermetallics: Complex Structures, Novel Clusters, and Intriguing Bonding with Pronounced Electron Delocalization.

    Science.gov (United States)

    Lin, Qisheng; Miller, Gordon J

    2018-01-16

    complexity can be realized by small amounts of Li replacing Zn atoms in the parent binary compounds CaZn 2 , CaZn 3 , and CaZn 5 ; their phase formation and bonding schemes can be rationalized by Fermi surface-Brillouin zone interactions between nearly free-electron states. "Cation-rich", electron-poor polar intermetallics have emerged using rare earth metals as the electropositive ("cationic") component together metal/metalloid clusters that mimic the backbones of aromatic hydrocarbon molecules, which give evidence of extensive electronic delocalization and multicenter bonding. Thus, we can identify three distinct, valence electron-poor, polar intermetallic systems that have yielded unprecedented phases adopting novel structures containing complex clusters and intriguing bonding characteristics. In this Account, we summarize our recent specific progress in the developments of novel Au-rich BaAl 4 -type related structures, shown in the "gold-rich grid", lithiation-modulated Ca-Li-Zn phases stabilized by different bonding characteristics, and rare earth-rich polar intermetallics containing unprecedented hydrocarbon-like planar Co-Ge metal clusters and pronounced delocalized multicenter bonding. We will focus mainly on novel structural motifs, bonding analyses, and the role of valence electrons for phase stability.

  6. Ligations of Gold Atoms with Iron Porphyrin

    DEFF Research Database (Denmark)

    Zhang, Ling; Kepp, Kasper Planeta; Ulstrup, Jens

    Gold is an exotic material with d-electrons deciding electronic mappings andconfigurations of adsorbed molecules. The specific interaction of Au atoms and S-, Ncappedmolecules make gold nanoparticles widely applied in the medicine transport andimmunoassay. Density functional theory demonstrates t...

  7. Metallic gold beads in hyaluronic acid

    DEFF Research Database (Denmark)

    Pedersen, Dan Sonne; Tran, Thao Phuong; Smidt, Kamille

    2013-01-01

    . In conclusion, our findings support that bio-liberation of gold from metallic gold surfaces have anti-inflammatory properties similar to classic gold compounds, warranting further studies into the pharmacological potential of this novel gold-treatment and the possible synergistic effects of hyaluronic acid....... by exploiting macrophage-induced liberation of gold ions (dissolucytosis) from gold surfaces. Injecting gold beads in hyaluronic acid (HA) as a vehicle into the cavities of the brain can delay clinical signs of disease progression in the MS model, experimental autoimmune encephalitis (EAE). This study...... investigates the anti-inflammatory properties of metallic gold/HA on the gene expression of tumor necrosis factor (Tnf-α), Interleukin (Il)-1β, Il-6, Il-10, Colony-stimulating factor (Csf)-v2, Metallothionein (Mt)-1/2, Bcl-2 associated X protein (Bax) and B cell lymphoma (Bcl)-2 in cultured J774 macrophages...

  8. Complexes of natural carbohydrates with metal cations

    International Nuclear Information System (INIS)

    Alekseev, Yurii E; Garnovskii, Alexander D; Zhdanov, Yu A

    1998-01-01

    Data on the interaction of natural carbohydrates (mono-, oligo-, and poly-saccharides, amino sugars, and natural organic acids of carbohydrate origin) with metal cations are surveyed and described systematically. The structural diversity of carbohydrate metal complexes, caused by some specific features of carbohydrates as ligands, is demonstrated. The influence of complex formation on the chemical properties of carbohydrates is discussed. It is shown that the formation of metal complexes plays an important role in the configurational and conformational analysis of carbohydrates. The practical significance of the coordination interaction in the series of carbohydrate ligands is demonstrated. The bibliography includes 571 references.

  9. Complex Macromolecular Architectures by Living Cationic Polymerization

    KAUST Repository

    Alghamdi, Reem D.

    2015-05-01

    Poly (vinyl ether)-based graft polymers have been synthesized by the combination of living cationic polymerization of vinyl ethers with other living or controlled/ living polymerization techniques (anionic and ATRP). The process involves the synthesis of well-defined homopolymers (PnBVE) and co/terpolymers [PnBVE-b-PCEVE-b-PSiDEGVE (ABC type) and PSiDEGVE-b-PnBVE-b-PSiDEGVE (CAC type)] by sequential living cationic polymerization of n-butyl vinyl ether (nBVE), 2-chloroethyl vinyl ether (CEVE) and tert-butyldimethylsilyl ethylene glycol vinyl ether (SiDEGVE), using mono-functional {[n-butoxyethyl acetate (nBEA)], [1-(2-chloroethoxy) ethyl acetate (CEEA)], [1-(2-(2-(t-butyldimethylsilyloxy)ethoxy) ethoxy) ethyl acetate (SiDEGEA)]} or di-functional [1,4-cyclohexanedimethanol di(1-ethyl acetate) (cHMDEA), (VEMOA)] initiators. The living cationic polymerizations of those monomers were conducted in hexane at -20 0C using Et3Al2Cl3 (catalyst) in the presence of 1 M AcOEt base.[1] The PCEVE segments of the synthesized block terpolymers were then used to react with living macroanions (PS-DPE-Li; poly styrene diphenyl ethylene lithium) to afford graft polymers. The quantitative desilylation of PSiDEGVE segments by n-Bu4N+F- in THF at 0 °C led to graft co- and terpolymers in which the polyalcohol is the outer block. These co-/terpolymers were subsequently subjected to “grafting-from” reactions by atom transfer radical polymerization (ATRP) of styrene to afford more complex macromolecular architectures. The base assisted living cationic polymerization of vinyl ethers were also used to synthesize well-defined α-hydroxyl polyvinylether (PnBVE-OH). The resulting polymers were then modified into an ATRP macro-initiator for the synthesis of well-defined block copolymers (PnBVE-b-PS). Bifunctional PnBVE with terminal malonate groups was also synthesized and used as a precursor for more complex architectures such as H-shaped block copolymer by “grafting-from” or

  10. Homogeneous cation exchange membrane by radiation grafting

    International Nuclear Information System (INIS)

    Kolhe, Shailesh M.; G, Agathian; Ashok Kumar

    2001-01-01

    Preparation of a strong cation exchange membrane by radiation grafting of styrene on to polyethylene (LDPE) film by mutual irradiation technique in the presence of air followed by sulfonation is described. The grafting has been carried out in the presence of air and without any additive. Low dose rate has been seen to facilitate the grafting. Further higher the grafting percentage more is the exchange capacity. The addition of a swelling agent during the sulfonation helped in achieving the high exchange capacity. The TGA-MASS analysis confirmed the grafting and the sulfonation. (author)

  11. Adsorption and Vibrational Study of Folic Acid on Gold Nanopillar Structures Using Surface-enhanced Raman Scattering Spectroscopy

    DEFF Research Database (Denmark)

    Castillo, John J.; Rindzevicius, Tomas; Rozo, Ciro E.

    2015-01-01

    on the nanopillars within the high electromagnetic field areas. The adsorption behaviour of folic acid and the band assignment of the main vibrations together with the optimized geometry of folic acid and folic acid in the presence of a cluster of 10 gold atoms were assessed using the density functional theory (B3......LYP(6-31G(d))) and the scalar relativistic effective core potential with a double-zeta basis set (LANL2DZ). The vibrations obtained from the solid-state folic acid and the folic acid on a gold cluster were in accordance with those observed experimentally. The analysis of the main vibrations indicated...

  12. The geology of the gold deposits of Prestea gold belt of Ghana ...

    African Journals Online (AJOL)

    This paper presents the geology of the gold deposits along the Prestea gold belt of Ghana to assist exploration work for new orebodies along the belt. Prestea district is the third largest gold producer in West Africa after Obuasi and Tarkwa districts (over 250 metric tonnes Au during the last century). The gold deposits are ...

  13. Gold Dispersion and Activation on the Basal Plane of Single-Layer MoS2

    KAUST Repository

    Merida, Cindy S.; Le, Duy; Echeverrí a, Elena M.; Nguyen, Ariana E.; Rawal, Takat B; Naghibi Alvillar, Sahar; Kandyba, Viktor; Al-Mahboob, Abdullah; Losovyj, Yaroslav B.; Katsiev, Khabiboulakh; Valentin, Michael D.; Huang, Chun-Yu; Gomez, Michael J.; Lu, I-Hsi; Guan, Alison; Barinov, Alexei; Rahman, Talat S; Dowben, Peter A.; Bartels, Ludwig

    2017-01-01

    Gold islands are typically associated with high binding affinity to adsorbates and catalytic activity. Here we present the growth of such dispersed nanoscale gold islands on single layer MoS2, prepared on an inert SiO2/Si support by chemical vapor deposition (CVD). This study offers a combination of growth process development, optical characterization, photoelectron spectroscopy at sub-micron spatial resolution, and advanced density functional theory modeling for detailed insight into the electronic interaction between gold and single-layer MoS2. In particular, we find the gold density of states in Au/MoS2/SiO2/Si to be far less well-defined than Au islands on other 2-dimensional materials such as graphene, for which we also provide data. We attribute this effect to the presence of heterogeneous Au adatom/MoS2-support interactions within the nanometer-scale gold cluster. As a consequence, theory predicts that CO will exhibit adsorption energies in excess of 1 eV at the Au cluster edges, where the local density of states is dominated by Au 5dz2 symmetry.

  14. Gold Dispersion and Activation on the Basal Plane of Single-Layer MoS2

    KAUST Repository

    Merida, Cindy S.

    2017-12-09

    Gold islands are typically associated with high binding affinity to adsorbates and catalytic activity. Here we present the growth of such dispersed nanoscale gold islands on single layer MoS2, prepared on an inert SiO2/Si support by chemical vapor deposition (CVD). This study offers a combination of growth process development, optical characterization, photoelectron spectroscopy at sub-micron spatial resolution, and advanced density functional theory modeling for detailed insight into the electronic interaction between gold and single-layer MoS2. In particular, we find the gold density of states in Au/MoS2/SiO2/Si to be far less well-defined than Au islands on other 2-dimensional materials such as graphene, for which we also provide data. We attribute this effect to the presence of heterogeneous Au adatom/MoS2-support interactions within the nanometer-scale gold cluster. As a consequence, theory predicts that CO will exhibit adsorption energies in excess of 1 eV at the Au cluster edges, where the local density of states is dominated by Au 5dz2 symmetry.

  15. Gold Nanoparticle Mediated Phototherapy for Cancer

    International Nuclear Information System (INIS)

    Yao, C.; Zhang, L.; Wang, J.; He, Y.; Xin, J.; Wang, S.; Xu, H.; Zhang, Z.

    2016-01-01

    Gold nanoparticles exhibit very unique physiochemical and optical properties, which now are extensively studied in range of medical diagnostic and therapeutic applications. In particular, gold nanoparticles show promise in the advancement of cancer treatments. This review will provide insights into the four different cancer treatments such as photothermal therapy, gold nanoparticle-aided photodynamic therapy, gold nanoparticle-aided radiation therapy, and their use as drug carrier. We also discuss the mechanism of every method and the adverse effects and its limitations

  16. Diversity among galaxy clusters

    International Nuclear Information System (INIS)

    Struble, M.F.; Rood, H.J.

    1988-01-01

    The classification of galaxy clusters is discussed. Consideration is given to the classification scheme of Abell (1950's), Zwicky (1950's), Morgan, Matthews, and Schmidt (1964), and Morgan-Bautz (1970). Galaxies can be classified based on morphology, chemical composition, spatial distribution, and motion. The correlation between a galaxy's environment and morphology is examined. The classification scheme of Rood-Sastry (1971), which is based on clusters's morphology and galaxy population, is described. The six types of clusters they define include: (1) a cD-cluster dominated by a single large galaxy, (2) a cluster dominated by a binary, (3) a core-halo cluster, (4) a cluster dominated by several bright galaxies, (5) a cluster appearing flattened, and (6) an irregularly shaped cluster. Attention is also given to the evolution of cluster structures, which is related to initial density and cluster motion

  17. Highly active thermally stable nanoporous gold catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Biener, Juergen; Wittstock, Arne; Biener, Monika M.; Bagge-Hansen, Michael; Baeumer, Marcus; Wichmann, Andre; Neuman, Bjoern

    2016-12-20

    In one embodiment, a system includes a nanoporous gold structure and a plurality of oxide particles deposited on the nanoporous gold structure; the oxide particles are characterized by a crystalline phase. In another embodiment, a method includes depositing oxide nanoparticles on a nanoporous gold support to form an active structure and functionalizing the deposited oxide nanoparticles.

  18. Gold and Silver Extraction from Leach Solutions

    OpenAIRE

    Bagdaulet K. Kenzhaliyev; Renata R. Iskhakova; Zamzagul D. Dosymbaeva; Esen N. Sulejmenov

    2014-01-01

    There has been carried out an investigation on the extraction of gold and silver from thiosulfate solutions: standard test and technological solutions of chemical and electrochemical leaching. The influence of related metals on the process of extracting gold from solution was studied. There has been conducted a comparative study of the IR spectra of solutions after the sorption of gold, silver and related metals.

  19. Cancer caused by radioactive gold rings

    International Nuclear Information System (INIS)

    Callary, E.M.

    1989-01-01

    Two recent cases of skin cancer caused by radioactive gold rings are described. The gold was contaminated with radon daughters from hollow goldseeds used to hold radon, back in the 1930s or possibly later. Other radioactive gold rings are probably being worn. The Canadian AECB offers free testing

  20. Linker-mediated assembly of gold nanoparticles into multimeric motifs

    Energy Technology Data Exchange (ETDEWEB)

    Sikora, Mateusz; Cieplak, Marek [Institute of Physics, Polish Academy of Sciences, Aleja Lotnikow 32/46, 02-668 Warsaw (Poland); Szymczak, Piotr [Institute of Theoretical Physics, Faculty of Physics, University of Warsaw, ulica Hoza 69, 00-681 Warsaw (Poland); Thompson, Damien, E-mail: mc@ifpan.edu.pl [Tyndall National Institute, Lee Maltings, University College Cork, Cork (Ireland)

    2011-11-04

    We present a theoretical description of linker-mediated self-assembly of gold nanoparticles (Au-NP). Using mesoscale simulations with a coarse-grained model for the Au NPs and dirhenium-based linker molecules, we investigate the conditions under which large clusters can grow and construct a phase diagram that identifies favorable growth conditions in terms of floating and bound linker concentrations. The findings can be considered as generic, as we expect other NP-linker systems to behave in a qualitatively similar way. In particular, we also discuss the case of antibody-functionalised Au NPs connected by the C-reactive proteins (CRPs). We extract some general rules for NP linking that may aid the production of size- and shape-specific NP clusters for technology applications.

  1. Cationic polymers in water treatment: Part 1: Treatability of water with cationic polymers

    Czech Academy of Sciences Publication Activity Database

    Polasek, P.; Mutl, Silvestr

    2002-01-01

    Roč. 28, č. 1 (2002), s. 69-82 ISSN 0378-4738 R&D Projects: GA AV ČR KSK2067107 Keywords : cationic polymers * treatability * water quality Subject RIV: BK - Fluid Dynamics Impact factor: 0.481, year: 2002

  2. Alkali Metal Cation versus Proton and Methyl Cation Affinities: Structure and Bonding Mechanism.

    Science.gov (United States)

    Boughlala, Zakaria; Fonseca Guerra, Célia; Bickelhaupt, F Matthias

    2016-06-01

    We have analyzed the structure and bonding of gas-phase Cl-X and [HCl-X](+) complexes for X(+)= H(+), CH3 (+), Li(+), and Na(+), using relativistic density functional theory (DFT). We wish to establish a quantitative trend in affinities of the anionic and neutral Lewis bases Cl(-) and HCl for the various cations. The Cl-X bond becomes longer and weaker along X(+) = H(+), CH3 (+), Li(+), and Na(+). Our main purpose is to understand the heterolytic bonding mechanism behind the intrinsic (i.e., in the absence of solvent) alkali metal cation affinities (AMCA) and how this compares with and differs from those of the proton affinity (PA) and methyl cation affinity (MCA). Our analyses are based on Kohn-Sham molecular orbital (KS-MO) theory in combination with a quantitative energy decomposition analysis (EDA) that pinpoints the importance of the different features in the bonding mechanism. Orbital overlap appears to play an important role in determining the trend in cation affinities.

  3. Ultrafast vibrations of gold nanorings

    DEFF Research Database (Denmark)

    Kelf, T; Tanaka, Y; Matsuda, O

    2011-01-01

    We investigate the vibrational modes of gold nanorings on a silica substrate with an ultrafast optical technique. By comparison with numerical simulations, we identify several resonances in the gigahertz range associated with axially symmetric deformations of the nanoring and substrate. We...

  4. Ultrafast vibrations of gold nanorings

    DEFF Research Database (Denmark)

    Kelf, T; Tanaka, Y; Matsuda, O

    2011-01-01

    We investigate the vibrational modes of gold nanorings on a silica substrate with an ultrafast optical technique. By comparison with numerical simulations, we identify several resonances in the gigahertz range associated with axially symmetric deformations of the nanoring and substrate. We elucid...

  5. Electron beam induced cationic polymerization of epoxy resins. Dependence of Tg on conversion

    International Nuclear Information System (INIS)

    Degrand, H.; Cazaux, F.; Coqueret, X.

    2002-01-01

    Complete text of publication follows. The high-energy radiation curing of monomer blends polymerizing by a free radical or by a cationic mechanism receives increasing attention in the perspective of high performance composite materials. In the present work, we have focused our attention on epoxy formulations as models of the matrices polymerizing by a cationic mechanism that could be used in fiber-reinforced composites for aerospace applications. We have examined the progress of the electron beam (EB) induced polymerization of diglycidylether of bisphenol A (DGEBA) in the presence of a diaryliodonium salt (DAIS) by FTIR spectroscopy and by dynamic mechanical thermal analysis (DMA). The obtained results allow to draw the gradual increase of the temperature for the network thermomechanical transition (T a , associated with the glass transition temperature T g ) over a broad range of conversion (p) and reveal a peculiar behavior at high conversion. In this domain (p > 0.90), the material's T g is shown to decrease when conversion approaches unity. Moreover, the post-irradiation thermal treatment of the materials, that generally yields effective 'dark curing', appears to induce a decrease of T g , with an amplitude correlated with the amount of DAIS in the formulation. Owing to the particular nature of the propagating centers in cationic polymerisation, the thermal relaxation of ionic clusters trapped in the glassy matrix can be reasonably invoked as a possible cause for this behavior

  6. Cobalt 60 cation exchange with mexican clays

    International Nuclear Information System (INIS)

    Nava Galve, R.G.

    1993-01-01

    Mexican clays can be used to remove radioactive elements from contaminated aqueous solutions. Cation exchange experiments were performed with 60 Co radioactive solution. In the present work the effect of contact time on the sorption of Co 2+ was studied. The contact time in hydrated montmorillonite was from 5 to 120 minutes and in dehydrated montmorillonite 5 to 1400 minutes. The Co 2+ uptake value was, in hydrated montmorillonite, between 0.3 to 0.85 m eq/g and in dehydrated montmorillonite, between 0.6 to 1.40 m eq/g. The experiments were done in a pH 5.1 to 5.7 and normal conditions. XRD patterns were used to characterize the samples. The crystallinity was determined by X-ray Diffraction and it was maintained before and after the cation exchange. DTA thermo grams showed the temperatures of the lost humidity and crystallization water. Finally, was observed that dehydrated montmorillonite adsorb more cobalt than hydrated montmorillonite. (Author)

  7. Cationic antimicrobial peptides in penaeid shrimp.

    Science.gov (United States)

    Tassanakajon, Anchalee; Amparyup, Piti; Somboonwiwat, Kunlaya; Supungul, Premruethai

    2011-08-01

    Penaeid shrimp aquaculture has been consistently affected worldwide by devastating diseases that cause a severe loss in production. To fight a variety of harmful microbes in the surrounding environment, particularly at high densities (of which intensive farming represents an extreme example), shrimps have evolved and use a diverse array of antimicrobial peptides (AMPs) as part of an important first-line response of the host defense system. Cationic AMPs in penaeid shrimps composed of penaeidins, crustins, and anti-lipopolysaccharide factors are comprised of multiple classes or isoforms and possess antibacterial and antifungal activities against different strains of bacteria and fungi. Shrimp AMPs are primarily expressed in circulating hemocytes, which is the main site of the immune response, and hemocytes expressing AMPs probably migrate to infection sites to fight against pathogen invasion. Indeed, most AMPs are produced as early as the nauplii developmental stage to protect shrimp larvae from infections. In this review, we discuss the sequence diversity, expression, gene structure, and antimicrobial activities of cationic AMPs in penaeid shrimps. The information available on antimicrobial activities indicates that these shrimp AMPs have potential therapeutic applications in the control of disease problems in aquaculture.

  8. Cationic Antimicrobial Polymers and Their Assemblies

    Science.gov (United States)

    Carmona-Ribeiro, Ana Maria; de Melo Carrasco, Letícia Dias

    2013-01-01

    Cationic compounds are promising candidates for development of antimicrobial agents. Positive charges attached to surfaces, particles, polymers, peptides or bilayers have been used as antimicrobial agents by themselves or in sophisticated formulations. The main positively charged moieties in these natural or synthetic structures are quaternary ammonium groups, resulting in quaternary ammonium compounds (QACs). The advantage of amphiphilic cationic polymers when compared to small amphiphilic molecules is their enhanced microbicidal activity. Besides, many of these polymeric structures also show low toxicity to human cells; a major requirement for biomedical applications. Determination of the specific elements in polymers, which affect their antimicrobial activity, has been previously difficult due to broad molecular weight distributions and random sequences characteristic of radical polymerization. With the advances in polymerization control, selection of well defined polymers and structures are allowing greater insight into their structure-antimicrobial activity relationship. On the other hand, antimicrobial polymers grafted or self-assembled to inert or non inert vehicles can yield hybrid antimicrobial nanostructures or films, which can act as antimicrobials by themselves or deliver bioactive molecules for a variety of applications, such as wound dressing, photodynamic antimicrobial therapy, food packing and preservation and antifouling applications. PMID:23665898

  9. Cationic Antimicrobial Polymers and Their Assemblies

    Directory of Open Access Journals (Sweden)

    Ana Maria Carmona-Ribeiro

    2013-05-01

    Full Text Available Cationic compounds are promising candidates for development of antimicrobial agents. Positive charges attached to surfaces, particles, polymers, peptides or bilayers have been used as antimicrobial agents by themselves or in sophisticated formulations. The main positively charged moieties in these natural or synthetic structures are quaternary ammonium groups, resulting in quaternary ammonium compounds (QACs. The advantage of amphiphilic cationic polymers when compared to small amphiphilic molecules is their enhanced microbicidal activity. Besides, many of these polymeric structures also show low toxicity to human cells; a major requirement for biomedical applications. Determination of the specific elements in polymers, which affect their antimicrobial activity, has been previously difficult due to broad molecular weight distributions and random sequences characteristic of radical polymerization. With the advances in polymerization control, selection of well defined polymers and structures are allowing greater insight into their structure-antimicrobial activity relationship. On the other hand, antimicrobial polymers grafted or self-assembled to inert or non inert vehicles can yield hybrid antimicrobial nanostructures or films, which can act as antimicrobials by themselves or deliver bioactive molecules for a variety of applications, such as wound dressing, photodynamic antimicrobial therapy, food packing and preservation and antifouling applications.

  10. Basic exchangeable cations in Finnish mineral soils

    Directory of Open Access Journals (Sweden)

    Armi Kaila

    1972-09-01

    Full Text Available The content of exchangeable Ca, Mg, K and Na replaced by neutral ammonium acetate was determined in 470 samples of mineral soils from various parts of Finland, except from Lapland. The amount of all these cations tended to increase with an increase in the clay content, but variation within each textural class was large, and the ranges usually overlapped those of the other classes. The higher acidity of virgin surface soils was connected with a lower average degree of saturation by Ca as compared with the corresponding textural classes of cultivated soils. No significant difference in the respective contents of other cations was detected. The samples of various textural groups from deeper layers were usually poorer in exchangeable Ca and K than the corresponding groups of plough layer. The mean content of exchangeable Mg was equal or even higher in the samples from deeper layers than in the samples from plough layer, except in the group of sand soils. The percentage of Mg of the effective CEC increased, as an average, from 9 in the sand and fine sand soils of plough layer to 30 in the heavy clay soils; in the heavy clay soils from deeper layers its mean value was 38 ± 4 %. In the samples of plough layer, the mean ratio of Ca to Mg in sand and fine sand soils was about 9, in silt and loam soils about 6, in the coarser clay soils about 4, and in heavy clay about 2.

  11. Lithium formate ion clusters formation during electrospray ionization: Evidence of magic number clusters by mass spectrometry and ab initio calculations

    International Nuclear Information System (INIS)

    Shukla, Anil; Bogdanov, Bogdan

    2015-01-01

    Small cationic and anionic clusters of lithium formate were generated by electrospray ionization and their fragmentations were studied by tandem mass spectrometry (collision-induced dissociation with N 2 ). Singly as well as multiply charged clusters were formed in both positive and negative ion modes with the general formulae, (HCOOLi) n Li + , (HCOOLi) n Li m m+ , (HCOOLi) n HCOO − , and (HCOOLi) n (HCOO) m m− . Several magic number cluster (MNC) ions were observed in both the positive and negative ion modes although more predominant in the positive ion mode with (HCOOLi) 3 Li + being the most abundant and stable cluster ion. Fragmentations of singly charged positive clusters proceed first by the loss of a dimer unit ((HCOOLi) 2 ) followed by the loss of monomer units (HCOOLi) although the former remains the dominant dissociation process. In the case of positive cluster ions, all fragmentations lead to the magic cluster (HCOOLi) 3 Li + as the most abundant fragment ion at higher collision energies which then fragments further to dimer and monomer ions at lower abundances. In the negative ion mode, however, singly charged clusters dissociated via sequential loss of monomer units. Multiply charged clusters in both positive and negative ion modes dissociated mainly via Coulomb repulsion. Quantum chemical calculations performed for smaller cluster ions showed that the trimer ion has a closed ring structure similar to the phenalenylium structure with three closed rings connected to the central lithium ion. Further additions of monomer units result in similar symmetric structures for hexamer and nonamer cluster ions. Thermochemical calculations show that trimer cluster ion is relatively more stable than neighboring cluster ions, supporting the experimental observation of a magic number cluster with enhanced stability

  12. Radiochemical study of isomerization of free butyl cations

    International Nuclear Information System (INIS)

    Sinotova, E.N.; Nefedov, V.D.; Skorokhodov, S.S.; Arkhipov, Yu.M.

    1987-01-01

    Ion-molecular reactions of free butyl cations, generated by nuclear chemical method, with carbon monoxide containing small quantities of ethanol vapors are studied. Carbon monoxide was used to fix instable butyl cations in the form of corresponding acyl ions. Ester of α-methyl-butyric acid appears to be the only product of free butyl cation interaction with carbon monoxide in the presence of ethanol vapors. That means, that up to the moment of butyl cation reaction with carbon monoxide, the primary butyl cations are almost completely isomerized into secondary in agreement with results of previous investigations. This allows one to study free butyl cation isomerization process according to ion-molecular reaction product isomeric composition

  13. What Makes Clusters Decline?

    DEFF Research Database (Denmark)

    Østergaard, Christian Richter; Park, Eun Kyung

    2015-01-01

    Most studies on regional clusters focus on identifying factors and processes that make clusters grow. However, sometimes technologies and market conditions suddenly shift, and clusters decline. This paper analyses the process of decline of the wireless communication cluster in Denmark. The longit...... but being quick to withdraw in times of crisis....

  14. Clustering of correlated networks

    OpenAIRE

    Dorogovtsev, S. N.

    2003-01-01

    We obtain the clustering coefficient, the degree-dependent local clustering, and the mean clustering of networks with arbitrary correlations between the degrees of the nearest-neighbor vertices. The resulting formulas allow one to determine the nature of the clustering of a network.

  15. Stability and recovery of DNA origami structure with cation concentration

    Science.gov (United States)

    Chen, Yi; Wang, Ping; Liu, Yang; Liu, Ting; Xu, Yan; Zhu, Shanshan; Zhu, Jun; Ye, Kai; Huang, Guang; Dannong, He

    2018-01-01

    We synthesized triangular and rectangular DNA origami nanostructures and investigated the stability and recovery of them under low cation concentration. Our results demonstrated that the origami nanostructures would melt when incubated in low cation concentration, and recover whilst kept in the concentration for less than 10 min. However, extending the incubation time would lead to irreversible melting. Our results show the possibility of application of DNA origami nanostructures for things such as a sensor for cation concentration response, etc.

  16. Relevant Subspace Clustering

    DEFF Research Database (Denmark)

    Müller, Emmanuel; Assent, Ira; Günnemann, Stephan

    2009-01-01

    Subspace clustering aims at detecting clusters in any subspace projection of a high dimensional space. As the number of possible subspace projections is exponential in the number of dimensions, the result is often tremendously large. Recent approaches fail to reduce results to relevant subspace...... clusters. Their results are typically highly redundant, i.e. many clusters are detected multiple times in several projections. In this work, we propose a novel model for relevant subspace clustering (RESCU). We present a global optimization which detects the most interesting non-redundant subspace clusters...... achieves top clustering quality while competing approaches show greatly varying performance....

  17. Tunnelling conductive hybrid films of gold nanoparticles and cellulose and their applications as electrochemical electrodes

    International Nuclear Information System (INIS)

    Liu, Zhiming; Wang, Xuefeng; Wu, Wenjian; Li, Mei

    2015-01-01

    Conductive hybrid films of metal nanoparticles and polymers have practical applications in the fields of sensing, microelectronics and catalysis, etc. Herein, we present the electrochemical availability of tunnelling conductive hybrid films of gold nanoparticles (GNPs) and cellulose. The hybrid films were provided with stable tunnelling conductive properties with 12 nm GNPs of 12.7% (in weight). For the first time, the conductive hybrid films were used as substrates of electrochemical electrodes to load calmodulin (CaM) proteins for sensing of calcium cations. The electrodes of hybrid films with 20 nm GNPs of 46.7% (in weight) exhibited stable electrochemical properties, and showed significant responses to calcium cations with concentrations as low as 10 −9 M after being loaded with CaM proteins. (paper)

  18. Surface vertical deposition for gold nanoparticle film

    International Nuclear Information System (INIS)

    Diao, J J; Qiu, F S; Chen, G D; Reeves, M E

    2003-01-01

    In this rapid communication, we present the surface vertical deposition (SVD) method to synthesize the gold nanoparticle films. Under conditions where the surface of the gold nanoparticle suspension descends slowly by evaporation, the gold nanoparticles in the solid-liquid-gas junction of the suspension aggregate together on the substrate by the force of solid and liquid interface. When the surface properties of the substrate and colloidal nanoparticle suspension define for the SVD, the density of gold nanoparticles in the thin film made by SVD only depends on the descending velocity of the suspension surface and on the concentration of the gold nanoparticle suspension. (rapid communication)

  19. [Biosynthesis of gold nanoparticles by Azospirillum brasilense].

    Science.gov (United States)

    Kupriashina, M A; Vetchinkina, E P; Burov, A M; Ponomareva, E G; Nikitina, V E

    2014-01-01

    Plant-associated nitrogen-fixing soil bacteria Azospirillum brasilense were shown to reduce the gold of chloroauric acid to elemental gold, resulting in formation of gold nanoparicles. Extracellular phenoloxidizing enzymes (laccases and Mn peroxidases) were shown to participate in reduction of Au+3 (HAuCl4) to Au(0). Transmission electron microscopy revealed accumulation of colloidal gold nanoparticles of diverse shape in the culture liquid of A. brasilense strains Sp245 and Sp7. The size of the electron-dense nanospheres was 5 to 50 nm, and the size of nanoprisms varied from 5 to 300 nm. The tentative mechanism responsible for formation of gold nanoparticles is discussed.

  20. Cluster ion beam facilities

    International Nuclear Information System (INIS)

    Popok, V.N.; Prasalovich, S.V.; Odzhaev, V.B.; Campbell, E.E.B.

    2001-01-01

    A brief state-of-the-art review in the field of cluster-surface interactions is presented. Ionised cluster beams could become a powerful and versatile tool for the modification and processing of surfaces as an alternative to ion implantation and ion assisted deposition. The main effects of cluster-surface collisions and possible applications of cluster ion beams are discussed. The outlooks of the Cluster Implantation and Deposition Apparatus (CIDA) being developed in Guteborg University are shown

  1. Calculating the enthalpy of vaporization for ionic liquid clusters.

    Science.gov (United States)

    Kelkar, Manish S; Maginn, Edward J

    2007-08-16

    Classical atomistic simulations are used to compute the enthalpy of vaporization of a series of ionic liquids composed of 1-alkyl-3-methylimidazolium cations paired with the bis(trifluoromethylsulfonyl)imide anion. The calculations show that the enthalpy of vaporization is lowest for neutral ion pairs. The enthalpy of vaporization increases by about 40 kJ/mol with the addition of each ion pair to the vaporizing cluster. Non-neutral clusters have much higher vaporization enthalpies than their neutral counterparts and thus are not expected to make up a significant fraction of volatile species. The enthalpy of vaporization increases slightly as the cation alkyl chain length increases and as temperature decreases. The calculated vaporization enthalpies are consistent with two sets of recent experimental measurements as well as with previous atomistic simulations.

  2. Gold and not so real gold in Medieval treatises

    Directory of Open Access Journals (Sweden)

    Srebrenka Bogovic-Zeskoski

    2015-01-01

    Full Text Available The aim of this study is to evidence diverse materials and processes used by artisans (and alchemists required to synthesize a visually viable replacement for gold. The emphasis of the research is upon the production of mosaic gold or porporina, a pigment that has survived into modern times, which was used as ink and as paint. Base metals, mostly tin, but also alloys were used both into foils coated with glazes and varnishes and as pigment. The research focuses upon recipes documented in treatises dating from Antiquity to the late Medieval period (ca. 1500 and an attempt is made to answer two questions. In the first place, why was there a need for a surrogate? Secondly, why are there so few tangible examples detected on surviving artifacts? In conclusion, an argument is offered pointing out that, although much can be learned by scientific examination of artifacts, textual analysis is equally important and necessary to unravel mysteries of ancient technologies

  3. Gold(I)-Alkanethiolate Nanotubes

    KAUST Repository

    Zhang, Yu Xin; Zeng, Hua Chun

    2009-01-01

    (Figure Presented) A solution approach to assembling Au(I) - alkanethiolates into nanotube structures at room temperature is presented, in which Au(I) cations and alkanethiolate ligands are coordinated into thin platelet forms that then evolve into an open tubular configuration (see figure). The organic-inorganic hybrid nature of the nanotubes, their ability to be modified, and their high stability make them of interest for practical applications. © 2009 WILEY-VCH Verlag GmbH & Co. KGaA.

  4. Gold(I)-Alkanethiolate Nanotubes

    KAUST Repository

    Zhang, Yu Xin

    2009-12-28

    (Figure Presented) A solution approach to assembling Au(I) - alkanethiolates into nanotube structures at room temperature is presented, in which Au(I) cations and alkanethiolate ligands are coordinated into thin platelet forms that then evolve into an open tubular configuration (see figure). The organic-inorganic hybrid nature of the nanotubes, their ability to be modified, and their high stability make them of interest for practical applications. © 2009 WILEY-VCH Verlag GmbH & Co. KGaA.

  5. Surfactant-Modified Ultrafine Gold Nanoparticles with Magnetic Responsiveness for Reversible Convergence and Release of Biomacromolecules.

    Science.gov (United States)

    Xu, Lu; Dong, Shuli; Hao, Jingcheng; Cui, Jiwei; Hoffmann, Heinz

    2017-03-28

    It is difficult to synthesize magnetic gold nanoparticles (AuNPs) with ultrafine sizes (coating AuNPs using magnetic particles, compounds, or ions. Here, magnetic cationic surfactants C 16 H 33 N + (CH 3 ) 3 [CeCl 3 Br] - (CTACe) and C 16 H 33 N + (CH 3 ) 3 [GdCl 3 Br] - (CTAGd) are prepared by a one-step coordination reaction, i.e., C 16 H 33 N + (CH 3 ) 3 Br - (CTABr) + CeCl 3 or GdCl 3 → CTACe or CTAGd. A simple strategy for fabricate ultrafine (gold nanoparticles (AuNPs) via surface modification with weak oxidizing paramagnetic cationic surfactants, CTACe or CTAGd, is developed. The resulting AuNPs can highly concentrate the charges of cationic surfactants on their surfaces, thereby presenting strong electrostatic interaction with negatively charged biomacromolecules, DNA, and proteins. As a consequence, they can converge DNA and proteins over 90% at a lower dosage than magnetic surfactants or existing magnetic AuNPs. The surface modification with these cationic surfactants endows AuNPs with strong magnetism, which allows them to magnetize and migrate the attached biomacromolecules with a much higher efficiency. The native conformation of DNA and proteins can be protected during the migration. Besides, the captured DNA and proteins could be released after adding sufficient inorganic salts such as at c NaBr = 50 mmol·L -1 . Our results could offer new guidance for a diverse range of systems including gene delivery, DNA transfection, and protein delivery and separation.

  6. PREFACE: Nuclear Cluster Conference; Cluster'07

    Science.gov (United States)

    Freer, Martin

    2008-05-01

    The Cluster Conference is a long-running conference series dating back to the 1960's, the first being initiated by Wildermuth in Bochum, Germany, in 1969. The most recent meeting was held in Nara, Japan, in 2003, and in 2007 the 9th Cluster Conference was held in Stratford-upon-Avon, UK. As the name suggests the town of Stratford lies upon the River Avon, and shortly before the conference, due to unprecedented rainfall in the area (approximately 10 cm within half a day), lay in the River Avon! Stratford is the birthplace of the `Bard of Avon' William Shakespeare, and this formed an intriguing conference backdrop. The meeting was attended by some 90 delegates and the programme contained 65 70 oral presentations, and was opened by a historical perspective presented by Professor Brink (Oxford) and closed by Professor Horiuchi (RCNP) with an overview of the conference and future perspectives. In between, the conference covered aspects of clustering in exotic nuclei (both neutron and proton-rich), molecular structures in which valence neutrons are exchanged between cluster cores, condensates in nuclei, neutron-clusters, superheavy nuclei, clusters in nuclear astrophysical processes and exotic cluster decays such as 2p and ternary cluster decay. The field of nuclear clustering has become strongly influenced by the physics of radioactive beam facilities (reflected in the programme), and by the excitement that clustering may have an important impact on the structure of nuclei at the neutron drip-line. It was clear that since Nara the field had progressed substantially and that new themes had emerged and others had crystallized. Two particular topics resonated strongly condensates and nuclear molecules. These topics are thus likely to be central in the next cluster conference which will be held in 2011 in the Hungarian city of Debrechen. Martin Freer Participants and Cluster'07

  7. Cation depletion by the sodium pump in red cells with pathologic cation leaks. Sickle cells and xerocytes.

    OpenAIRE

    Joiner, C H; Platt, O S; Lux, S E

    1986-01-01

    The mechanism by which sickle cells and xerocytic red cells become depleted of cations in vivo has not been identified previously. Both types of cells exhibit elevated permeabilities to sodium and potassium, in the case of sickle cells, when deoxygenated. The ouabain-insensitive fluxes of sodium and potassium were equivalent, however, in both cell types under these conditions. When incubated 18 hours in vitro, sickle cells lost cations but only when deoxygenated. This cation depletion was blo...

  8. Nanotoxicity of gold and gold-cobalt nanoalloy.

    Science.gov (United States)

    Girgis, E; Khalil, W K B; Emam, A N; Mohamed, M B; Rao, K V

    2012-05-21

    Nanotoxicology test of gold nanoparticles (Au NPs) and gold-cobalt (Au-Co) nanoalloy is an important step in their safety evaluation for biomedical applications. The Au and Au-Co NPs were prepared by reducing the metal ions using sodium borohydride (NaBH(4)) in the presence of polyvinyl pyrrolidone (PVP) as a capping material. The average size and shape of the nanoparticles (NPs) were characterized using high resolution transmission electron microscopy (HRTEM). Cobalt presence in the nanoalloy was confirmed by energy dispersive X-ray spectroscopy (EDX) analysis, and the magnetic properties of these particles were determined using a vibrating sample magnetometer (VSM). The Gold and gold-cobalt NPs of average size 15 ± 1.5 nm were administered orally to mice with a dose of 80, 160, and 320 mg/kg per body weight (bw) using gavages. Samples were collected after 7 and 14 days of the treatment. The results indicated that the Au-Co NPs were able to induce significant alteration in the tumor-initiating genes associated with an increase of micronuclei (MNs) formation and generation of DNA adduct (8-hydroxy-2-deoxyguanosine, 8-OHdG) as well as a reduction in the glutathione peroxidase activity. This action of Au-Co NPs was observed using 160 and 320 mg/kg bw at both time intervals. However, Au NPs had much lower effects than Au-Co NPs on alteration in the tumor-initiating genes, frequency of MNs, and generation of 8-OHdG as well as glutathione peroxidase activity except with the highest dose of Au NPs. This study suggests that the potential to cause in vivo genetic and antioxidant enzyme alterations due to the treatment by Au-Co nanoalloy may be attributed to the increase in oxidative stress in mice.

  9. Predicting Organic Cation Sorption Coefficients: Accounting for Competition from Sorbed Inorganic Cations Using a Simple Probe Molecule.

    Science.gov (United States)

    Jolin, William C; Goyetche, Reaha; Carter, Katherine; Medina, John; Vasudevan, Dharni; MacKay, Allison A

    2017-06-06

    With the increasing number of emerging contaminants that are cationic at environmentally relevant pH values, there is a need for robust predictive models of organic cation sorption coefficients (K d ). Current predictive models fail to account for the differences in the identity, abundance, and affinity of surface-associated inorganic exchange ions naturally present at negatively charged receptor sites on environmental solids. To better understand how organic cation sorption is influenced by surface-associated inorganic exchange ions, sorption coefficients of 10 organic cations (including eight pharmaceuticals and two simple probe organic amines) were determined for six homoionic forms of the aluminosilicate mineral, montmorillonite. Organic cation sorption coefficients exhibited consistent trends for all compounds across the various homoionic clays with sorption coefficients (K d ) decreasing as follows: K d Na + > K d NH 4 + ≥ K d K + > K d Ca 2+ ≥ K d Mg 2+ > K d Al 3+ . This trend for competition between organic cations and exchangeable inorganic cations is consistent with the inorganic cation selectivity sequence, determined for exchange between inorganic ions. Such consistent trends in competition between organic and inorganic cations suggested that a simple probe cation, such as phenyltrimethylammonium or benzylamine, could capture soil-to-soil variations in native inorganic cation identity and abundance for the prediction of organic cation sorption to soils and soil minerals. Indeed, sorption of two pharmaceutical compounds to 30 soils was better described by phenyltrimethylammonium sorption than by measures of benzylamine sorption, effective cation exchange capacity alone, or a model from the literature (Droge, S., and Goss, K. Environ. Sci. Technol. 2013, 47, 14224). A hybrid approach integrating structural scaling factors derived from this literature model of organic cation sorption, along with phenyltrimethylammonium K d values, allowed for

  10. Computational study of cation substitutions in apatites

    International Nuclear Information System (INIS)

    Tamm, Toomas; Peld, Merike

    2006-01-01

    Density-functional theory plane-wave modeling of fluor- and hydroxyapatites has been performed, where one or two calcium ions per unit cell were replaced with cadmium or zinc cations. It was found that cadmium ions favor Ca(1) positions in fluorapatites and Ca(2) positions in hydroxyapatites, in agreement with experiment. A similar pattern is predicted for zinc substitutions. In the doubly substituted cases, where only hydroxyapatites were modeled, a preference for the substituting ions to be located in Ca(2) position was also observed. Displacement of the hydroxide ions from their symmetrical positions on the hexagonal axis can be used to explain the preferred configurations of substituting ions around the axis. -- Deformation of the hydroxide ion chain due to substitutions around the ion channel in substituted hydroxyapatites

  11. Retention of Cationic Starch onto Cellulose Fibres

    Science.gov (United States)

    Missaoui, Mohamed; Mauret, Evelyne; Belgacem, Mohamed Naceur

    2008-08-01

    Three methods of cationic starch titration were used to quantify its retention on cellulose fibres, namely: (i) the complexation of CS with iodine and measurement of the absorbency of the ensuing blue solution by UV-vis spectroscopy; (ii) hydrolysis of the starch macromolecules followed by the conversion of the resulting sugars to furan-based molecules and quantifying the ensuing mixture by measuring their absorbance at a Ι of 490 nm, using the same technique as previous one and; finally (iii) hydrolysis of starch macromolecules by trifluoro-acetic acid and quantification of the sugars in the resulting hydrolysates by high performance liquid chromatography. The three methods were found to give similar results within the range of CS addition from 0 to 50 mg per g of cellulose fibres.

  12. Repurposing Cationic Amphiphilic Antihistamines for Cancer Treatment

    DEFF Research Database (Denmark)

    Ellegaard, Anne-Marie; Dehlendorff, Christian; Vind, Anna C.

    2016-01-01

    Non-small cell lung cancer (NSCLC) is one of the deadliest cancers worldwide. In search for new NSCLC treatment options, we screened a cationic amphiphilic drug (CAD) library for cytotoxicity against NSCLC cells and identified several CAD antihistamines as inducers of lysosomal cell death. We...... then performed a cohort study on the effect of CAD antihistamine use on mortality of patients diagnosed with non-localized cancer in Denmark between 1995 and 2011. The use of the most commonly prescribed CAD antihistamine, loratadine, was associated with significantly reduced all-cause mortality among patients...... with non-localized NSCLC or any non-localized cancer when compared with use of non-CAD antihistamines and adjusted for potential confounders. Of the less frequently described CAD antihistamines, astemizole showed a similar significant association with reduced mortality as loratadine among patients with any...

  13. Use of a material conducting hydrogen cations

    International Nuclear Information System (INIS)

    Howe, A.T.; Shilton, M.G.

    1986-01-01

    The invention concerns a separator conducting hydrogenous for electrical devices, which contains at least one compound with the formula H(UO 2 )PO 4 x nH 2 O, H(UO 2 )AsO 4 x nH 2 O or H(UO 2 )IO 4 (OH) 2 x nH 2 O, where not more than 50% by weight of the H + is replaced by one or more cations, such as Li + , Na + , K + , NH 4 + , Cu 2+ , Mg 2+ , Ca 2+ , Ba 2+ , Sr 2+ , Pb 2+ , Fe 2+ , Co 2+ , Ni 2+ , Mn 2+ or Al 3+ . The electrical device having the separator can be an electrolysis cell, for example, an electro chromium cell. (H x WO 3 ), a hydrogen isotope enrichment device, a proton-sensitive electrode (eg for a pH meter), a battery or a fuel cell. (orig./MM) [de

  14. A Cationic Smart Copolymer for DNA Binding

    Directory of Open Access Journals (Sweden)

    Tânia Ribeiro

    2017-11-01

    Full Text Available A new block copolymer with a temperature-responsive block and a cationic block was prepared by reversible addition-fragmentation chain transfer (RAFT polymerization, with good control of its size and composition. The first block is composed by di(ethylene glycol methyl ether methacrylate (DEGMA and oligo(ethylene glycol methyl ether methacrylate (OEGMA, with the ratio DEGMA/OEGMA being used to choose the volume phase transition temperature of the polymer in water, tunable from ca. 25 to above 90 °C. The second block, of trimethyl-2-methacroyloxyethylammonium chloride (TMEC, is positively charged at physiological pH values and is used for DNA binding. The coacervate complexes between the block copolymer and a model single strand DNA are characterized by fluorescence correlation spectroscopy and fluorescence spectroscopy. The new materials offer good prospects for biomedical application, for example in controlled gene delivery.

  15. Hydration Structure of the Quaternary Ammonium Cations

    KAUST Repository

    Babiaczyk, Wojtek Iwo

    2010-11-25

    Two indicators of the hydropathicity of small solutes are introduced and tested by molecular dynamics simulations. These indicators are defined as probabilities of the orientation of water molecules\\' dipoles and hydrogen bond vectors, conditional on a generalized distance from the solute suitable for arbitrarily shaped molecules. Using conditional probabilities, it is possible to distinguish features of the distributions in close proximity of the solute. These regions contain the most significant information on the hydration structure but cannot be adequately represented by using, as is usually done, joint distance-angle probability densities. Our calculations show that using our indicators a relative hydropathicity scale for the interesting test set of the quaternary ammonium cations can be roughly determined. © 2010 American Chemical Society.

  16. Calixarenes synthesized for seducing and trapping cations

    International Nuclear Information System (INIS)

    Dozol, J.F.

    1997-01-01

    Calixarenes are known to be selective extractants for cesium radioactive cations. This liquid-liquid extraction is still to be studied and would allow to reduce the volume of years living radioactive wastes before they were stored and perhaps to remove then the cesium by transmutation. Calixarenes are macrocycles with phenolic units bridged by methylene groups. They have the important property to have a flexible structure. On this basic structure, all kinds of chemical functions can be branched. They thus confer particular properties to the molecule. A computerized virtual construction phase of molecules is actually studied in order to optimize the extraction. It is currently known that with small modifications it will be possible to selectively extract heavy metals (Hg, Cd..) coming from industrial pollution. (O.M.)

  17. Molecular oxygen adsorption and dissociation on Au12M clusters with M = Cu, Ag or Ir

    Science.gov (United States)

    Jiménez-Díaz, Laura M.; Pérez, Luis A.

    2018-03-01

    In this work, we present a density functional theory study of the structural and electronic properties of isolated neutral clusters of the type Au12M, with M = Cu, Ag, or Ir. On the other hand, there is experimental evidence that gold-silver, gold-copper and gold-iridium nanoparticles have an enhanced catalytic activity for the CO oxidation reaction. In order to address these phenomena, we also performed density functional calculations of the adsorption and dissociation of O2 on these nanoparticles. Moreover, to understand the effects of Cu, Ag, and Ir impurity atoms on the dissociation of O2, we also analyze this reaction in the corresponding pure gold cluster. The results indicate that the substitution of one gold atom in a Au13 cluster by Ag, Cu or Ir diminishes the activation energy barrier for the O2 dissociation by nearly 1 eV. This energy barrier is similar for Au12Ag and Au12Cu, whereas for Au12Ir is even lower. These results suggest that the addition of other transition metal atoms to gold nanoclusters can enhance their catalytic activity towards the CO oxidation reaction, independently of the effect that the substrate could have on supported nanoclusters.

  18. Safety evaluation of cation-exchange resins

    International Nuclear Information System (INIS)

    Kalkwarf, D.R.

    1977-08-01

    Results are presented of a study to evaluate whether sufficient information is available to establish conservative limits for the safe use of cation-exchange resins in separating radionuclides and, if not, to recommend what new data should be acquired. The study was also an attempt to identify in-line analytical techniques for the evaluation of resin degradation during radionuclide processing. The report is based upon a review of the published literature and upon discussions with many people engaged in the use of these resins. It was concluded that the chief hazard in the use of cation-exchange resins for separating radionuclides is a thermal explosion if nitric acid or other strong oxidants are present in the process solution. Thermal explosions can be avoided by limiting process parameters so that the rates of heat and gas generation in the system do not exceed the rates for their transfer to the surroundings. Such parameters include temperature, oxidant concentration, the amounts of possible catalysts, the radiation dose absorbed by the resin and the diameter of the resin column. Current information is not sufficient to define safe upper limits for these parameters. They can be evaluated, however, from equations derived from the Frank-Kamenetskii theory of thermal explosions provided the heat capacities, thermal conductivities and rates of heat evolution in the relevant resin-oxidant mixtures are known. It is recommended that such measurements be made and the appropriate limits be evaluated. A list of additional safety precautions are also presented to aid in the application of these limits and to provide additional margins of safety. In-line evaluation of resin degradation to assess its safety hazard is considered impractical. Rather, it is recommended that the resin be removed from use before it has received the limiting radiation dose, evaluated as described above

  19. Anaerobic toxicity of cationic silver nanoparticles

    International Nuclear Information System (INIS)

    Gitipour, Alireza; Thiel, Stephen W.; Scheckel, Kirk G.; Tolaymat, Thabet

    2016-01-01

    The microbial toxicity of silver nanoparticles (AgNPs) stabilized with different capping agents was compared to that of Ag"+ under anaerobic conditions. Three AgNPs were investigated: (1) negatively charged citrate-coated AgNPs (citrate-AgNPs), (2) minimally charged polyvinylpyrrolidone coated AgNPs (PVP-AgNPs) and (3) positively charged branched polyethyleneimine coated AgNPs (BPEI-AgNPs). The AgNPs investigated in this experiment were similar in size (10–15 nm), spherical in shape, but varied in surface charge which ranged from highly negative to highly positive. While, at AgNPs concentrations lower than 5 mg L"−"1, the anaerobic decomposition process was not influenced by the presence of the nanoparticles, there was an observed impact on the diversity of the microbial community. At elevated concentrations (100 mg L"−"1 as silver), only the cationic BPEI-AgNPs demonstrated toxicity similar in magnitude to that of Ag"+. Both citrate and PVP-AgNPs did not exhibit toxicity at the 100 mg L"−"1 as measured by biogas evolution. These findings further indicate the varying modes of action for nanoparticle toxicity and represent one of the few studies that evaluate end-of-life management concerns with regards to the increasing use of nanomaterials in our everyday life. These findings also highlight some of the concerns with a one size fits all approach to the evaluation of environmental health and safety concerns associated with the use of nanoparticles. - Highlights: • At concentrations -1 the anaerobic decomposition process was not impacted. • An impact on the microbial community at concentrations -1 were observed. • At high concentrations (100 mg L"−"1), the cationic BPEI-AgNPs demonstrated toxicity. • Toxicity was demonstrated without the presence of oxidative dissolution of silver. • A one size fits all approach for the evaluation of NPs may not be accurate.

  20. Structural and optical properties of Si-doped Ag clusters

    KAUST Repository

    Mokkath, Junais Habeeb

    2014-03-06

    The structural and optical properties of AgN and Ag N-1Si1 (neutral, cationic, and anionic) clusters (N = 5 to 12) are systematically investigated using the density functional based tight binding method and time-dependent density functional theory, providing insight into recent experiments. The gap between the highest occupied and lowest unoccupied molecular orbitals and therefore the optical spectrum vary significantly under Si doping, which enables flexible tuning of the chemical and optical properties of Ag clusters. © 2014 American Chemical Society.

  1. Structural and optical properties of Si-doped Ag clusters

    KAUST Repository

    Mokkath, Junais Habeeb; Schwingenschlö gl, Udo

    2014-01-01

    The structural and optical properties of AgN and Ag N-1Si1 (neutral, cationic, and anionic) clusters (N = 5 to 12) are systematically investigated using the density functional based tight binding method and time-dependent density functional theory, providing insight into recent experiments. The gap between the highest occupied and lowest unoccupied molecular orbitals and therefore the optical spectrum vary significantly under Si doping, which enables flexible tuning of the chemical and optical properties of Ag clusters. © 2014 American Chemical Society.

  2. Management of cluster headache

    DEFF Research Database (Denmark)

    Tfelt-Hansen, Peer C; Jensen, Rigmor H

    2012-01-01

    The prevalence of cluster headache is 0.1% and cluster headache is often not diagnosed or misdiagnosed as migraine or sinusitis. In cluster headache there is often a considerable diagnostic delay - an average of 7 years in a population-based survey. Cluster headache is characterized by very severe...... or severe orbital or periorbital pain with a duration of 15-180 minutes. The cluster headache attacks are accompanied by characteristic associated unilateral symptoms such as tearing, nasal congestion and/or rhinorrhoea, eyelid oedema, miosis and/or ptosis. In addition, there is a sense of restlessness...... and agitation. Patients may have up to eight attacks per day. Episodic cluster headache (ECH) occurs in clusters of weeks to months duration, whereas chronic cluster headache (CCH) attacks occur for more than 1 year without remissions. Management of cluster headache is divided into acute attack treatment...

  3. Symmetries of cluster configurations

    International Nuclear Information System (INIS)

    Kramer, P.

    1975-01-01

    A deeper understanding of clustering phenomena in nuclei must encompass at least two interrelated aspects of the subject: (A) Given a system of A nucleons with two-body interactions, what are the relevant and persistent modes of clustering involved. What is the nature of the correlated nucleon groups which form the clusters, and what is their mutual interaction. (B) Given the cluster modes and their interaction, what systematic patterns of nuclear structure and reactions emerge from it. Are there, for example, families of states which share the same ''cluster parents''. Which cluster modes are compatible or exclude each other. What quantum numbers could characterize cluster configurations. There is no doubt that we can learn a good deal from the experimentalists who have discovered many of the features relevant to aspect (B). Symmetries specific to cluster configurations which can throw some light on both aspects of clustering are discussed

  4. Distribution and composition of gold in porphyry gold systems: example from the Biely Vrch deposit, Slovakia

    Science.gov (United States)

    Koděra, Peter; Kozák, Jaroslav; Brčeková, Jana; Chovan, Martin; Lexa, Jaroslav; Jánošík, Michal; Biroň, Adrián; Uhlík, Peter; Bakos, František

    2018-03-01

    The Biely Vrch deposit in the Western Carpathians is assigned to the shallow, sulfide-poor porphyry gold deposit type and has an exceptionally low Cu/Au ratio. According to 3-D geochemical models, there is a limited spatial correlation between Au and Cu due to the primary introduction of gold by a salt melt and Cu by low-density vapor. Despite a rough spatial correlation of gold grades with quartz stockwork intensity, gold is hosted mostly by altered rock, exclusively in native form. Three main gold mineral assemblages were recognized here. In the deepest parts of the system, the K- and Ca-Na silicate gold assemblage is associated with minerals of high-temperature alteration (plagioclase, K-feldspar, actinolite), with gold grades and fineness depending on depth and potassium content of the host rock: K-silicate alteration hosts the lowest fineness gold ( 914), whereas Ca-Na silicate alteration has the highest ( 983). The intermediate argillic gold assemblage is the most widespread, with gold hosted mainly by chlorite, illite, smectite, and interstratified illite-chlorite-smectite minerals. The gold fineness is mostly variable (875-990) and inherited from the former gold mineral assemblages. The latest advanced argillic gold assemblage has its gold mostly in kaolinite. The extremely high fineness ( 994) results from gold remobilization by late-stage aqueous magmatic-hydrothermal fluids. Uncommon bonanza-grade appears where the earlier gold mineral assemblages were further enriched by this remobilized gold. Primary precipitation of gold occurred during ascent and cooling of salt melts at 450 to 309 °C, mostly during retrograde quartz solubility.

  5. Byzantine gold coins and jewellery

    International Nuclear Information System (INIS)

    Oddy, A.; La Niece, S.

    1986-01-01

    The article deals with the dating of Byzantine gold coinage. The results of such a study are of fundamental importance for the study of the economic history of the later Byzantine Empire and they are also of importance for the historian of technology when studying the composition of the contemporary Byzantine jewellery. Although Carbon-14 dating cannot be used as a method af dating, historians can still benefit from the analysis of the alloy of which the antiquity is made, as this is sometimes characteristic of the period in which it was used. A number of pieces of Byzantine jewellery has been analysed by x-ray fluorescence analysis, after first gently abrading a small area of the surface of the gold with the carborundum paper in an inconspicious position on the back or side of the object. A table is given on the results of this analysis

  6. Reverse Transfection Using Gold Nanoparticles

    Science.gov (United States)

    Yamada, Shigeru; Fujita, Satoshi; Uchimura, Eiichiro; Miyake, Masato; Miyake, Jun

    Reverse transfection from a solid surface has the potential to deliver genes into various types of cell and tissue more effectively than conventional methods of transfection. We present a method for reverse transfection using a gold colloid (GC) as a nanoscaffold by generating nanoclusters of the DNA/reagentcomplex on a glass surface, which could then be used for the regulation of the particle size of the complex and delivery of DNA into nuclei. With this method, we have found that the conjugation of gold nanoparticles (20 nm in particle size) to the pEGFP-N1/Jet-PEI complex resulted in an increase in the intensity of fluorescence of enhanced green fluorescent protein (EGFP) (based on the efficiency of transfection) from human mesenchymal stem cells (hMSCs), as compared with the control without GC. In this manner, we constructed a method for reverse transfection using GC to deliver genes into the cells effectively.

  7. CMS Industries awarded gold, crystal

    CERN Multimedia

    2006-01-01

    The CMS collaboration honoured 10 of its top suppliers in the seventh annual awards ceremony The representatives of the firms that recieved the CMS Gold and Crystal Awards stand with their awards after the ceremony. The seventh annual CMS Awards ceremony was held on Monday 13 March to recognize the industries that have made substantial contributions to the construction of the collaboration's detector. Nine international firms received Gold Awards, and General Tecnica of Italy received the prestigious Crystal Award. Representatives from the companies attended the ceremony during the plenary session of CMS week. 'The role of CERN, its machines and experiments, beyond particle physics is to push the development of equipment technologies related to high-energy physics,'said CMS Awards Coordinator Domenico Campi. 'All of these industries must go beyond the technologies that are currently available.' Without the involvement of good companies over the years, the construction of the CMS detector wouldn't be possible...

  8. Nanobubble trouble on gold surfaces

    DEFF Research Database (Denmark)

    Holmberg, Maria; Kuhle, A.; Garnaes, J.

    2003-01-01

    When analyzing surfaces related to biosensors with in situ atomic force microscopy (AFM), the existence of nanobubbles called for our attention. The bubbles seem to form spontaneously when gold surfaces are immersed in clean water and are probably a general phenomenon at water-solid interfaces....... Besides from giving rise to undesired effects in, for example, biosensors, nanobubbles can also cause artifacts in AFM imaging. We have observed nanobubbles on unmodified gold surfaces, immersed in clean water, using standard silicon AFM probes. Nanobubbles can be made to disappear from contact mode AFM...... images and then to reappear by changing the scanning force. By combining contact mode AFM imaging and local force measurements, the interaction between the nanobubbles and the probe can be analyzed and give information about the characteristics of nanobubbles. A model of the forces between the AFM probe...

  9. Gold, currencies and market efficiency

    Czech Academy of Sciences Publication Activity Database

    Krištoufek, Ladislav; Vošvrda, Miloslav

    2016-01-01

    Roč. 449, č. 1 (2016), s. 27-34 ISSN 0378-4371 R&D Projects: GA ČR(CZ) GBP402/12/G097 Institutional support: RVO:67985556 Keywords : Efficient market hypothesis, * Gold * Currencies, * Fractal dimension * Entropy * Long-Term memory Subject RIV: AH - Economics Impact factor: 2.243, year: 2016 http://library.utia.cas.cz/separaty/2016/E/kristoufek-0455876.pdf

  10. Ground Optical Lightning Detector (GOLD)

    Science.gov (United States)

    Jackson, John, Jr.; Simmons, David

    A photometer developed to characterize lightning from the ground is discussed. The detector and the electronic signal processing and data storage systems are presented along with field data measured by the system. The discussion will include improvements that will be incorporated to enhance the measurement of lightning and the data storage capability to record for many days without human involvement. Finally, the calibration of the GOLD system is presented.

  11. Extinction Coefficient of Gold Nanostars

    OpenAIRE

    de Puig, Helena; Tam, Justina O.; Yen, Chun-Wan; Gehrke, Lee; Hamad-Schifferli, Kimberly

    2015-01-01

    Gold nanostars (NStars) are highly attractive for biological applications due to their surface chemistry, facile synthesis and optical properties. Here, we synthesize NStars in HEPES buffer at different HEPES/Au ratios, producing NStars of different sizes and shapes, and therefore varying optical properties. We measure the extinction coefficient of the synthesized NStars at their maximum surface plasmon resonances (SPR), which range from 5.7 × 108 to 26.8 × 108 M−1cm−1. Measured values correl...

  12. Biomolecular Assembly of Gold Nanocrystals

    Energy Technology Data Exchange (ETDEWEB)

    Micheel, Christine Marya [Univ. of California, Berkeley, CA (United States)

    2005-05-20

    Over the past ten years, methods have been developed to construct discrete nanostructures using nanocrystals and biomolecules. While these frequently consist of gold nanocrystals and DNA, semiconductor nanocrystals as well as antibodies and enzymes have also been used. One example of discrete nanostructures is dimers of gold nanocrystals linked together with complementary DNA. This type of nanostructure is also known as a nanocrystal molecule. Discrete nanostructures of this kind have a number of potential applications, from highly parallel self-assembly of electronics components and rapid read-out of DNA computations to biological imaging and a variety of bioassays. My research focused in three main areas. The first area, the refinement of electrophoresis as a purification and characterization method, included application of agarose gel electrophoresis to the purification of discrete gold nanocrystal/DNA conjugates and nanocrystal molecules, as well as development of a more detailed understanding of the hydrodynamic behavior of these materials in gels. The second area, the development of methods for quantitative analysis of transmission electron microscope data, used computer programs written to find pair correlations as well as higher order correlations. With these programs, it is possible to reliably locate and measure nanocrystal molecules in TEM images. The final area of research explored the use of DNA ligase in the formation of nanocrystal molecules. Synthesis of dimers of gold particles linked with a single strand of DNA possible through the use of DNA ligase opens the possibility for amplification of nanostructures in a manner similar to polymerase chain reaction. These three areas are discussed in the context of the work in the Alivisatos group, as well as the field as a whole.

  13. Gold Nanocages for Biomedical Applications**

    OpenAIRE

    Skrabalak, Sara E.; Chen, Jingyi; Au, Leslie; Lu, Xianmao; Li, Xingde; Xia, Younan

    2007-01-01

    Nanostructured materials provide a promising platform for early cancer detection and treatment. Here we highlight recent advances in the synthesis and use of Au nanocages for such biomedical applications. Gold nanocages represent a novel class of nanostructures, which can be prepared via a remarkably simple route based on the galvanic replacement reaction between Ag nanocubes and HAuCl4. The Au nanocages have a tunable surface plasmon resonance peak that extends into the near-infrared, where ...

  14. Organic cation rhodamines for screening organic cation transporters in early stages of drug development.

    Science.gov (United States)

    Ugwu, Malachy C; Oli, Angus; Esimone, Charles O; Agu, Remigius U

    The aim of this study was to investigate the suitability of rhodamine-123, rhodamine-6G and rhodamine B as non-radioactive probes for characterizing organic cation transporters in respiratory cells. Fluorescent characteristics of the compounds were validated under standard in vitro drug transport conditions (buffers, pH, and light). Uptake/transport kinetics and intracellular accumulation of the compounds were investigated. Uptake/transport mechanisms were investigated by comparing the effect of pH, temperature, concentration, polarity, OCTs/OCTNs inhibitors/substrates, and metabolic inhibitors on the cationic dyes uptake in Calu-3 cells. Fluorescence stability and intensity of the compounds were altered by buffer composition, light, and pH. Uptake of the dyes was concentration-, temperature- and pH-dependent. OCTs/OCTNs inhibitors significantly reduced intracellular accumulation of the compounds. Whereas rhodamine-B uptake was sodium-dependent, pH had no effect on rhodamine-123 and rhodamine-6G uptake. Transport of the dyes across the cells was polarized: (AP→BL>BL→AP transport) and saturable: {V max =14.08±2.074, K m =1821±380.4 (rhodamine-B); V max =6.555±0.4106, K m =1353±130.4 (rhodamine-123) and V max =0.3056±0.01402, K m =702.9±60.97 (rhodamine-6G)}. The dyes were co-localized with MitoTracker®, the mitochondrial marker. Cationic rhodamines, especially rhodamine-B and rhodamine- 6G can be used as organic cation transporter substrates in respiratory cells. During such studies, buffer selection, pH and light exposure should be taken into consideration. Copyright © 2016 Elsevier Inc. All rights reserved.

  15. Unconventional hydrogen bonding to organic ions in the gas phase: Stepwise association of hydrogen cyanide with the pyridine and pyrimidine radical cations and protonated pyridine

    Energy Technology Data Exchange (ETDEWEB)

    Hamid, Ahmed M.; El-Shall, M. Samy, E-mail: mselshal@vcu.edu [Department of Chemistry, Virginia Commonwealth University, Richmond, Virginia 23284 (United States); Hilal, Rifaat; Elroby, Shaaban; Aziz, Saadullah G. [Department of Chemistry, Faculty of Science, King Abdulaziz University, Jeddah 21589 (Saudi Arabia)

    2014-08-07

    Equilibrium thermochemical measurements using the ion mobility drift cell technique have been utilized to investigate the binding energies and entropy changes for the stepwise association of HCN molecules with the pyridine and pyrimidine radical cations forming the C{sub 5}H{sub 5}N{sup +·}(HCN){sub n} and C{sub 4}H{sub 4}N{sub 2}{sup +·}(HCN){sub n} clusters, respectively, with n = 1–4. For comparison, the binding of 1–4 HCN molecules to the protonated pyridine C{sub 5}H{sub 5}NH{sup +}(HCN){sub n} has also been investigated. The binding energies of HCN to the pyridine and pyrimidine radical cations are nearly equal (11.4 and 12.0 kcal/mol, respectively) but weaker than the HCN binding to the protonated pyridine (14.0 kcal/mol). The pyridine and pyrimidine radical cations form unconventional carbon-based ionic hydrogen bonds with HCN (CH{sup δ+}⋯NCH). Protonated pyridine forms a stronger ionic hydrogen bond with HCN (NH{sup +}⋯NCH) which can be extended to a linear chain with the clustering of additional HCN molecules (NH{sup +}⋯NCH··NCH⋯NCH) leading to a rapid decrease in the bond strength as the length of the chain increases. The lowest energy structures of the pyridine and pyrimidine radical cation clusters containing 3-4 HCN molecules show a strong tendency for the internal solvation of the radical cation by the HCN molecules where bifurcated structures involving multiple hydrogen bonding sites with the ring hydrogen atoms are formed. The unconventional H-bonds (CH{sup δ+}⋯NCH) formed between the pyridine or the pyrimidine radical cations and HCN molecules (11–12 kcal/mol) are stronger than the similar (CH{sup δ+}⋯NCH) bonds formed between the benzene radical cation and HCN molecules (9 kcal/mol) indicating that the CH{sup δ+} centers in the pyridine and pyrimidine radical cations have more effective charges than in the benzene radical cation.

  16. Jabiluka gold-uranium project

    International Nuclear Information System (INIS)

    1988-01-01

    The Jabiluka gold-uranium deposit, 230km east of Darwin in the Alligator Rivers Region of the Northern Territory, was discovered by Pancontinental Mining Limited in 1971. Jabiluka, with reserves in excess of 200,000 tonnes of contained U 3 O 8 in two deposits 500 metres apart, is the world's largest high grade uranium deposit and also contains nearly 12 tonnes of gold. It is proposed that only the larger deposit, Jabiluka II will be mined - by underground extraction methods, and that 275,000 tonnes of ore per year will be mined and processed to produce 1,500 tonnes of U 3 O 8 and up to 30,000 oz of gold. The revenue from the uranium sales is estimated to be of the order of A$100 million per year at A$30/lb. By the end of 1982 all necessary mining and environmental approvals had been obtained and significant marketing progress made. With the Australian Labor Party winning Commonwealth Government in the 1983 election, Pancontinental's permission to seek sales contracts was withdrawn and development of the Jabiluka deposit ceased. Jabiluka remains undeveloped - awaiting a change in Australian Government policy on uranium. figs., maps

  17. Analysis of gold and silver concentration on gold mining tailings by neutron activation analysis

    International Nuclear Information System (INIS)

    Sadikov, I.I.; Salimov, M.I.; Sadykova, Z.O.

    2014-01-01

    Full text: Instrumental neutron-activation analysis without radiochemical separation is one of most applicable and often used methods to analyze the concentration of gold, silver and other rare and noble metals in gold ores. This method is not suitable for analyzing low concentration of gold and silver in gold mining tailings due to rather high concentration of some elements. Samples are dissolved by boiling in a mixture of concentrated hydrochloric and nitric acids to extract gold and silver into the solution. Chemical yield of gold and silver after dissolution of the sample and further chromatographic separation is between 92 and 95 percent respectively

  18. Effects of metallic cations in the beryl flotation

    International Nuclear Information System (INIS)

    Lima Leonel, C.M. de; Peres, A.E.C.

    1984-01-01

    The beryl zeta potential in microelectrophoretic cell is studied in the presence of neutral electrolyte, cations of calcium, magnesium and iron. The petroleum sulfonate is used how collector in Hallimond tube. Hydroxy complex of metallic cations seems activate the ore and precipitates of colloidal metallic hidroxies seems lower him when added to the mixture. (M.A.C.) [pt

  19. Stable polyfluorinated cycloalkenyl cations and their NMR spectra

    International Nuclear Information System (INIS)

    Snegirev, V.F.; Galakhov, M.V.; Makarov, K.N.; Bakhmutov, V.I.

    1986-01-01

    New stable 1-methoxyperfluoro-2-ethylcyclobutenyl, 1-methoxyperfluoro-2-methylcyclo-pentenyl, and 1-methoxyperfluoro-2-ethylcyclohexenyl cations were obtained by the action of antimony pentafluoride on the corresponding olefins. The distribution of the charges in the investigated polyfluorinated cycloalkenyl cations was investigated by 13 C NMR method

  20. Synthesis of Cationic Core-Shell Latex Particles

    NARCIS (Netherlands)

    Dziomkina, N.; Hempenius, Mark A.; Vancso, Gyula J.

    2006-01-01

    Surfactant-free seeded (core-shell) polymerization of cationic polymer colloids is presented. Polystyrene core particles with sizes between 200 nm and 500 nm were synthesized. The number average diameter of the colloidal core particles increased with increasing monomer concentration. Cationic shells